Compositions and methods containing fluorine substituted olefins

ABSTRACT

Various uses of fluorinated alkenes, particularly HFO-1234 and HFCO-1233zd in a variety of applications, including refrigeration, foams, blowing agents, aerosols, propellants, solvent compositions, fire extinguishing and suppressing agents, extraction agents and catalyst deposition are disclosed.

RELATED APPLICATIONS

The present application is a Continuation-in-Part of and claims thepriority benefit of each of U.S. Provisional Application No. 61/020,390filed Jan. 10, 2008 and U.S. Provisional Application No. 61/049,393filed Apr. 30, 2008, each of which is incorporated herein by referenceas if fully set forth herein.

The present application is also related to as follows to, claims thebenefit of and incorporates by reference each of the following UnitedStates Patent Applications: a Continuation-in-Part of U.S. patentapplication Ser. No. 11/475,605, filed Jun. 25, 2006, now U.S. Pat. No.9,005,467; a Continuation-in-Part of U.S. patent application Ser. No.12/276,137, filed Nov. 21, 2006, now abandoned, which claims the benefitof U.S. Provisional Patent Application No. 60/989,977, filed Nov. 25,2007; a Continuation-in-Part of U.S. patent application Ser. No.11/474,887, filed Jun. 26, 2006, now pending, and a Continuation-in-Partof PCT Patent Application No. PCT/US07/64570, filed Mar. 21, 2007.

FIELD OF THE INVENTION

This invention relates to compositions, methods and systems havingutility in numerous applications, including particularly heat transfersystems, such as refrigeration systems, blowing agents, foamablecompositions, foams and articles made with or from foams. In preferredaspects, the present invention is directed to such compositions whichcomprise at least one multi-fluorinated olefin and at least oneadditional component which is either another multi-fluorinated olefin oranother compound which is not a multi-fluorinated olefin.

BACKGROUND

Fluorocarbon based fluids have found widespread use in many commercialand industrial applications, including as the working fluid in systemssuch as air conditioning, heat pump and refrigeration systems, asaerosol propellants, as blowing agents, as heat transfer media, and asgaseous dielectrics. Because of certain suspected environmentalproblems, including the relatively high global warming potentials,associated with the use of some of the compositions that have heretoforebeen used in these applications, it has become increasingly desirable touse fluids having low or even zero ozone depletion potential, such ashydrofluorocarbons (“HFCs”). Thus, the use of fluids that do not containchlorofluorocarbons (“CFCs”) or hydrochlorofluorocarbons (“HCFCs”) isdesirable. Furthermore, some HFC fluids may have relatively high globalwarming potentials associated therewith, and it is desirable to usehydrofluorocarbon or other fluorinated fluids having as low globalwarming potentials as possible while maintaining the desired performancein use properties. Additionally, the use of single component fluids orazeotrope-like mixtures, which do not substantially fractionate onboiling and evaporation, is desirable in certain circumstances.

Certain fluorocarbons have been a preferred component in many heatexchange fluids, such as refrigerants, for many years in manyapplications. For, example, fluoroalkanes, such as chlorofluoromethaneand chlorofluoroethane derivatives, have gained widespread use asrefrigerants in applications including air conditioning and heat pumpapplications owing to their unique combination of chemical and physicalproperties. Many of the refrigerants commonly utilized in vaporcompression systems are either single components fluids or azeotropicmixtures.

As suggested above, concern has been increasing in recent years aboutpotential damage to the earth's atmosphere and climate, and certainchlorine-based compounds have been identified as particularlyproblematic in this regard. The use of chlorine-containing compositions(such as chlorofluorocarbons (CFC's), hydrochlorofluorocarbons (HCF's)and the like) as the working fluid in heat transfer systems, such as inrefrigeration and air-conditioning systems, has become disfavoredbecause of the ozone-depleting properties associated with many of suchcompounds. There has thus been an increasing need for new fluorocarbonand hydrofluorocarbon compounds and compositions that are attractivealternatives to the compositions heretofore used in these and otherapplications. For example, it has become desirable to retrofitchlorine-containing systems, such as blowing agent systems orrefrigeration systems by replacing chlorine-containing compounds withnon-chlorine-containing compounds that will not deplete the ozone layer,such as hydrofluorocarbons (HFC's). Industry in general, and the heattransfer and blowing agent segments of industry in particular arecontinually seeking new fluorocarbon based mixtures that offeralternatives to, and are considered environmentally safer substitutesfor, CFCs and HCFCs. It is generally considered important, in manycases, however, that any potential substitute must also possess thoseproperties present in many of the most widely used of such materials,such as excellent heat transfer properties, appropriate chemicalstability, low- or no-toxicity, non-flammability and/or lubricantcompatibility, among others, and other desirable foam characteristicswhen used as blowing agents,.

Applicants have come to appreciate that lubricant compatibility is ofparticular importance in many of applications. More particularly, it ishighly desirably for refrigeration fluids to be compatible with thelubricant utilized in the compressor unit, used in most refrigerationsystems. Unfortunately, many non-chlorine-containing refrigerationfluids, including HFC's, are relatively insoluble and/or immiscible inthe types of lubricants used traditionally with CFC's and HFC's,including, for example, mineral oils, alkylbenzenes orpoly(alpha-olefins). In order for a refrigeration fluid/lubricantcombination to work at a desirable level of efficiency within acompression refrigeration, air-conditioning and/or heat pump system, thelubricant should be sufficiently soluble in the refrigeration liquidover a wide range of operating temperatures. Such solubility lowers theviscosity of the lubricant and allows it to flow more easily throughoutthe system. In the absence of such solubility, lubricants tend to becomelodged in the coils of the evaporator of the refrigeration,air-conditioning or heat pump system, as well as other parts of thesystem, and thus reduce the system efficiency.

With regard to efficiency in use, it is important to note that a loss inrefrigerant thermodynamic performance or energy efficiency may havesecondary environmental impacts through increased fossil fuel usagearising from an increased demand for electrical energy.

Furthermore, it is generally considered desirably for CFC refrigerantand blowing agent substitutes to be effective without major engineeringchanges to conventional systems, such as vapor compression technologyand foam generating systems.

Methods and compositions for making conventional foamed materials, suchas for example thermoplastic materials and thermosetting materials, havelong been known. These methods and compositions have typically utilizedchemical and/or physical blowing agents to form the foamed structure ina polymeric matrix. Such blowing agents have included, for example, azocompounds, various volatile organic compounds (VOCs) andchlorofluorocarbons (CFCs). The chemical blowing agents typicallyundergo some form of chemical change, including chemical reaction withthe material that forms the polymer matrix (usually at a predeterminedtemperature/pressure) that causes the release of a gas, such asnitrogen, carbon dioxide, or carbon monoxide. One of the most frequentlyused chemical blowing agents is water. The physical blowing agentstypically are dissolved in the polymer or polymer precursor material andthen expand volumetrically (again at a predeterminedtemperature/pressure) to contribute to the formation of the foamedstructure. Physical blowing agents are frequently used in connectionwith thermoplastic foams, although chemical blowing agents can be usedin place of or in addition to physical blowing agents in connection withthermoplastic foam. For example, it is known to use chemical blowingagents in connection with the formation of polyvinylchloride-basedfoams. It is common to use chemical blowing and/or physical blowingagents in connection with thermosetting foams. Of course, it is possiblethat certain compounds and the compositions that contain them may atonce constitute a chemical and a physical blowing agent.

It was common in the past that the CFCs were used as standard blowingagents in the preparation of isocyanate-based foams, such as rigid andflexible polyurethane and polyisocyanurate foams. For example,compositions consisting of CFC materials, such as CCl₃F (CFC-11) hadbecome a standard blowing agent. However, the use of this material hasbeen banned by international treaty on the grounds that its release intothe atmosphere damages the ozone layer in the stratosphere. As aconsequence, it is no longer generally common that neat CFC-11 is usedas a standard blowing agent for forming thermosetting foams, such asisocyanate-based foams and phenolic foams.

Flammability is another important property for many applications. Thatis, it is considered either important or essential in many applications,including particularly in heat transfer and blowing agent applications,to use compositions which are of low flammability or are non-flammable.Thus, it is frequently beneficial to use in such compositions compoundswhich are nonflammable. As used herein, the term “nonflammable” refersto compounds or compositions which are determined to be nonflammable asdetermined in accordance with ASTM standard E-681, dated 2002, which isincorporated herein by reference. Unfortunately, many HFC's which mightotherwise be desirable for used in refrigerant or foam blowing agentcompositions are not nonflammable. For example, the fluoroalkanedifluoroethane (HFC-152a) and the fluoroalkene 1,1,1-trifluorpropene(HFO-1243zf) are each flammable and therefore not viable for use in manyapplications.

Higher fluoroalkenes, that is fluorine-substituted alkenes having atleast five carbon atoms, have been suggested for use as refrigerants.U.S. Pat. No. 4,788,352—Smutny is directed to production of fluorinatedC₅ to C₈ compounds having at least some degree of unsaturation. TheSmutny patent identifies such higher olefins as being known to haveutility as refrigerants, pesticides, dielectric fluids, heat transferfluids, solvents, and intermediates in various chemical reactions. (Seecolumn 1, lines 11-22).

Another example of a relatively flammable material is the fluorinatedether 1,1,22-tetrafluoroethyl methyl ether (which is referred to asHFE-254pc or also sometimes as HFE-254cb), which has been measured tohave a flammability limit (vol %) of from about 5.4% to about 24.4%.Fluorinated ethers of this general type have been disclosed for use asblowing agents in U.S. Pat. No. 5,137,932—Beheme et al, which isincorporated herein by reference.

It has been suggested to use bromine-containing halocarbon additives todecrease flammability of certain materials, including foam blowingagents, in U.S. Pat. No. 5,900,185—Tapscott. The additives in thispatent are said to be characterized by high efficiency and shortatmospheric lifetimes, that is, low ozone depletion potential (ODP) anda low global warming potential (GWP).

It is believed that the olefins described in Smutny and Tapscott havecertain disadvantages. For example, some of these compounds may tend toattack substrates, particularly general-purpose plastics such as acrylicresins and ABS resins. Furthermore, the higher olefinic compoundsdescribed in Smutny may also be undesirable in certain applicationsbecause of the potential level of toxicity of such compounds which mayarise as a result of pesticide activity noted in Smutny. Also, suchcompounds may have a boiling point which is too high to make them usefulas a refrigerant in certain applications.

Bromofluoromethane and bromochlorofluoromethane derivatives,particularly bromotrifluoromethane (Halon 1301) andbromochlorodifluoromethane (Halon 1211) have gained widespread use asfire extinguishing agents in enclosed areas such as airplane cabins andcomputer rooms. However, the use of various halons is being phased outdue to their high ozone depletion. Moreover, as halons are frequentlyused in areas where humans are present, suitable replacements must alsobe safe to humans at concentrations necessary to suppress or extinguishfire.

Applicants have thus come to appreciate a need for compositions, andparticularly heat transfer compositions, fire extinguishing/suppressioncompositions, blowing agents, solvent compositions, and compatabilizingagents, that are potentially useful in numerous applications, includingvapor compression heating and cooling systems and methods, whileavoiding one or more of the disadvantages noted above.

SUMMARY

Applicants have found that the above-noted need, and other needs, can besatisfied by compositions, including heat transfer compositions, blowingagent compositions, foams and foam premixes, comprising one or more C3to C6 fluorakenes, and more preferably one or more C3, C4, or C5fluoroalkenes, preferably compounds having Formula I as follows:XCF_(z)R_(3-z)  (I)where X is a C₂, C₃, C₄ or C₅ unsaturated, substituted or unsubstituted,radical, each R is independently Cl, F, Br, I or H, and z is 1 to 3. Incertain preferred embodiments, the fluoroalkene of the present inventionhas at least four (4) halogen substituents, at least three of which areF. Preferably in certain embodiments none of the substituents are Br. Incertain preferred embodiments, the compound of Formula I comprises acompound, and preferably a three carbon compound, in which eachnon-terminal unsaturated carbon has at least one halogen substituent,more preferably at least one substituent selected from chlorine andfluorine, with compounds having at least three flourines and onechlorine being especially preferred in certain embodiments.

In certain preferred embodiments, especially embodiments involving heattransfer compositions and blowing agent compositions, the compound ofFormula I is a three carbon olefin in which z is 1 or 2. Thus, thecompound of Formula I in certain embodiments especially embodimentsinvolving heat transfer compositions and blowing agent compositions,comprises a compound of Formula (IA):CF_(w)H_(2-w)═CR—CF_(z)R_(3-z)  (IA)

where each R is independently Cl, F, Br, I or H, w is 1 or 2, and z is 1or 2.

In certain preferred compounds of Formula IA each R is F or H, examplesof which are:

-   -   CF₂═CF—CH₂F (HFO-1234yc)    -   CF₂═CH—CF₂H (HFO-1234zc)    -   Trans-CHF═CF—CF₂H (HFO-1234ye(E))    -   Cis-CHF═CF—CF₂H (HFO-1234ye(Z)).

In certain preferred embodiments, particularly blowing agentcompositions, the compositions include at least one compound of Formula(IA) in which at least one R, and even more preferably at least on R onthe saturated terminal carbon, is Cl.

For embodiments of Formula (IA) in which at least one Br substituent ispresent, it is preferred that the compound includes no hydrogen. In suchembodiments it also generally preferred that the Br substituent is on anunsaturated carbon, and even more preferably the Br substituent is on annon-terminal unsaturated carbon. One particularly preferred embodimentin this class is CF₃CBr═CF₂, including all of its isomers.

In certain embodiments it is highly preferred that the compounds ofFormula I comprise propenes, butenes, pentenes and hexenes having from 3to 5 fluorine substituents, with other substituents being either presentor not present. In certain preferred embodiments, no R is Br, andpreferably the unsaturated radical contains no Br substituents. Amongthe propenes, tetrafluoropropenes (HFO-1234) and fluorochloroporpenes(such as trifluoro,monochloropropenes (HFCO-1233), and even morepreferably CF₃CCl═CH₂ (HFCO-1233xf) and CF₃CH═CHCl (HFCO-1233zd)) areespecially preferred in certain embodiments.

In certain embodiments, pentafluoropropenes are preferred, includingparticularly those pentafluoropropenes in which there is a hydrogensubstituent on the terminal unsaturated carbon, such as CF₃CF═CFH(HFO-1225yez and/or yz), particularly since applicants have discoveredthat such compounds have a relatively low degree of toxicity incomparison to at least the compound CF₃CH═CF₂(HFO-1225zc).

Among the butenes, fluorochlorobutenes are especially preferred incertain embodiments.

The term “HFO-1234” is used herein to refer to all tetrafluoropropenes.Among the tetrafluoropropenes are included 1,1,1,2-tetrafluoropropene(HFO-1234yf), both cis- and trans-1,1,1,3-tetrafluoropropene(HFO-1234ze), CF₂═CF—CH₂F (HFO-1234yc), CF₂═CH—CF₂H (HFO-1234zc),trans-CHF═CF—CF₂H (HFO-1234ye(E)), and cis-CHF═CF—CF₂H (HFO-1234ye(Z)).The term HFO-1234ze is used herein generically to refer to1,1,1,3-tetrafluoropropene, independent of whether it is the cis- ortrans-form. The terms “cisHFO-1234ze” and “transHFO-1234ze” are usedherein to describe the cis- and trans-forms of1,1,1,3-tetrafluoropropene respectively. The term “HFO-1234ze” thereforeincludes within its scope cisHFO-1234ze, transHFO-1234ze, and allcombinations and mixtures of these. The term HFO-1234ye is used hereingenerically to refer to 1,2,3,3-tetrafluoropropene (CHF═CF—CF₂H),independent of whether it is the cis- or trans-form. The terms“cisHFO-1234ye” and “transHFO-1234ye” are used herein to describe thecis- and trans-forms of 1,2,3,3-tetrafluoropropene, respectively. Theterm “HFO-1234ye” therefore includes within its scope cisHFO-1234ye,transHFO-1234ye, and all combinations and mixtures of these.

The term “HFO-1233” is used herein to refer to alltrifluoro,monochloropropenes. Among the trifluoro,monochloropropenes areincluded 1,1,1,trifluoro-2,chloro-propene (HFCO-1233xf), and both cis-and trans-1,1,1-trifluo-3,chlororopropene (HFCO-1233zd). The termHFCO-1233zd is used herein generically to refer to1,1,1-trifluo-3,chloro-propene, independent of whether it is the cis- ortrans-form. The terms “cisHFCO-1233zd” and “transHFCO-1233zd” are usedherein to describe the cis- and trans-forms of1,1,1-trifluo,3-chlororopropene, respectively. The term “HFCO-1233zd”therefore includes within its scope cisHFCO-1233zd, transHFCO-1233zd,and all combinations and mixtures of these in all proportions andratios.

The term “HFO-1225” is used herein to refer to all pentafluoropropenes.Among such molecules are included 1,1,1,2,3 pentafluoropropene(HFO-1225yez), both cis- and trans-forms thereof. The term HFO-1225yezis thus used herein generically to refer to 1,1,1,2,3pentafluoropropene, independent of whether it is the cis- or trans-form.The term “HFO-1225yez” therefore includes within its scopecisHFO-1225yez, transHFO-1225yez, and all combinations and mixtures ofthese.

In certain preferred embodiments, the present compositions comprise acombination of two or more compounds of Formula I. In one such preferredembodiment the composition comprises at least one tetrafluoropropene andat least one pentafluoropropene compound, preferably with each compoundbeing present in the composition in an amount of from about 20% byweight to about 80% by weight, more preferably from about 30% by weightto about 70% by weight, and even more preferably from about 40% byweight to about 60% by weight. In certain of such embodiments, thetetrafluoropropene comprises, and preferably consists essentially ofHFO-1234 (most preferably HFO-1234yf) and HFO1225 (most preferablyHFO-1225yez). In another such preferred embodiment the compositioncomprises at least one monochlorotrifluoropropene compound and at leastone other fluorinated olefin, including tetrafluoropropene, with eachcompound being present in the composition in an amount of from about 20%by weight to about 80% by weight, more preferably from about 30% byweight to about 70% by weight, and even more preferably from about 40%by weight to about 60% by weight.

The present invention provides also methods and systems which utilizethe compositions of the present invention. In one aspect the methodsinclude methods and systems for heat transfer, for retrofitting existingheat transfer equipment, and for replacing the existing heat transferfluids in an existing heat transfer system. In other aspects the presentcompositions are used in connection with foams, foam blowing, formingfoams and foam premixes, solvating, flavor and fragrance extractionand/or delivery, aerosol generation, non-aerosol propellants and asinflating agents.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The Compositions

The preferred embodiments of the present invention are directed tocompositions comprising at least one fluoroalkene containing from 3 to 6carbon atoms, preferably 3 to 5 carbon atoms, and in certain highlypreferred embodiments three carbon atoms, and at least one carbon-carbondouble bond. The fluoroalkene compounds of the present invention aresometimes referred to herein for the purpose of convenience ashydrofluoro-olefins or “HFOs” if they contain at least one hydrogen.Although it is contemplated that the HFOs of the present invention maycontain two carbon-carbon double bonds, such compounds at the presenttime are not considered to be preferred. For HFOs which also contain atleast one chlorine atom, the designation HFCO is sometimes used herein

As mentioned above, the present compositions comprise one or morecompounds in accordance with Formula I, including each of the compoundsspecifically identified above. In certain preferred embodiments, thecompositions include compounds of Formula II below:

where each R is independently Cl, F, Br, I or H,

R′ is (CR₂)_(n)Y,

Y is CRF₂

and n is 0, 1, 2 or 3, preferably 0 or 1, it being generally preferredhowever that when Br is present in the compound there is no hydrogen inthe compound. In certain embodiments, Br is not present in the compound.

In highly preferred embodiments, Y is CF₃, n is 0 or 1 (most preferably0) and at least one of the remaining Rs is F, and preferably no R is Bror when Br is present, there is no hydrogen in the compound.

Applicants believe that, in general, the compounds of the aboveidentified Formulas I, IA, and II, and particularly those compoundsspecifically identified above, are generally effective and exhibitutility in each of the applications mentioned above, includingparticularly in heat transfer compositions such as refrigerantcompositions) and as blowing agent compositions, compatiblizers,aerosols, propellants, fragrances, flavor formulations, solventcompositions and inflating agent compositions. However, applicants havesurprisingly and unexpectedly found that certain of the compounds havinga structure in accordance with the formulas described above exhibit ahighly desirable low level of toxicity compared to other of suchcompounds. As can be readily appreciated, this discovery is ofpotentially enormous advantage and benefit for the formulation of notonly refrigerant compositions, but also any and all compositions whichwould otherwise contain relatively toxic compounds satisfying theformulas described above. More particularly, applicants believe that arelatively low toxicity level is associated with compounds of FormulaII, preferably wherein Y is CF₃, n is 0 or 1, wherein at least one R onthe unsaturated terminal carbon is H. Preferably in such preferredembodiments of Formula II wherein at least one R on the unsaturatedterminal carbon is H, at least one of the remaining Rs is F or Cl. It isalso preferred in certain embodiments, particularly when toxicity is ofparticular concern, that there is not more than one fluorinesubstituent, and even more preferably not more than one halogensubstituent, on the unsaturated terminal carbon. Applicants believe alsothat all structural, geometric and stereoisomers of such compounds areeffective and of beneficially low toxicity.

In certain preferred embodiments the compounds of the present inventioncomprise one or more C3 or C4 HFO, preferably a C3 HFO. In certainembodiments C4 HFOs are preferably used, including compounds inaccordance with Formula I in which X is a halogen substituted C₃alkylene and z is 3. In certain of such embodiments X is fluorine and/orchlorine substituted C₃ alkylene, with the following C₃ alkyleneradicals being preferred in certain embodiments:—CH═CF—CH₃—CF═CH—CH₃—CH₂—CF═CH₂—CH₂—CH=CFH,Such embodiments therefore comprise the following preferred compounds:CF₃—CH═CF—CH₃; CF₃—CF═CH—CH₃; CF₃—CH₂—CF═CH₂; CF₃—CH₂—CH═CFH; andcombinations of these with one another and/or with other compounds inaccordance with Formula I,

In certain preferred embodiments, the compound of the present inventioncomprises a C3 or C4 HFCO, preferably a C3 HFCO, and more preferably acompound in accordance with Formula II in which Y is CF₃, n is 0, atleast one R on the unsaturated terminal carbon is H, and at least one ofthe remaining Rs is Cl. HFCO-1233 is an example of such a preferredcompound.

In highly preferred embodiments, especially embodiments which comprisethe low toxicity compounds described above, n is zero. In certain highlypreferred embodiments the compositions of the present invention compriseone or more tetrafluoropropenes, including HFO-1234yf, (cis)HFO-1234zeand (trans)HFO-1234ze, with HFO-1234ze being generally preferred.Although the properties of (cis)HFO-1234ze and (trans)HFO-1234ze differin at least some respects, it is contemplated that each of thesecompounds is adaptable for use, either alone or together with othercompounds including its stereo isomer, in connection with each of theapplications, methods and systems described herein. For example,(trans)HFO-1234ze may be preferred for use in certain systems because ofits relatively low boiling point (−19° C.), while (cis)HFO-1234ze, witha boiling point of +9° C., may be preferred in other applications. Ofcourse, it is likely that combinations of the cis- and trans-isomerswill be acceptable and/or preferred in many embodiments. Accordingly, itis to be understood that the terms “HFO-1234ze” and1,3,3,3-tetrafluoropropene refer to both stereo isomers, and the use ofthis term is intended to indicate that each of the cis-and trans-formsapplies and/or is useful for the stated purpose unless otherwiseindicated.

HFO-1234 compounds are known materials and are listed in ChemicalAbstracts databases. The production of fluoropropenes such as CF₃CH═CH₂by catalytic vapor phase fluorination of various saturated andunsaturated halogen-containing C₃ compounds is described in U.S. Pat.Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is incorporatedherein by reference. EP 974,571, also incorporated herein by reference,discloses the preparation of 1,1,1,3-tetrafluoropropene by contacting1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with achromium-based catalyst at elevated temperature, or in the liquid phasewith an alcoholic solution of KOH, NaOH, Ca(OH)₂ or Mg(OH)₂. Inaddition, methods for producing compounds in accordance with the presentinvention are described generally in connection with pending UnitedStates Patent Application entitled “Process for ProducingFluorpropenes”, which is also incorporated herein by reference.

Other preferred compounds for use in accordance with the presentinvention include pentafluoropropenes, including all isomers thereof(eg., HFO-1225), tetra- and penta-fluorobutenes, including all isomersthereof (eg., HFO-1354 and HFO-1345). Of course, the presentcompositions may comprise combinations of any two or more compoundswithin the broad scope of the invention or within any preferred scope ofthe invention.

The present compositions, particularly those comprising HFCO-1233 and/orHFO-1234 (including HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc,HFO-1234ye(E), HFO-1234ye(Z), HFCO-1233xf, transHFCO-1233zd andcisHFCO-1233zd), are believed to possess properties that areadvantageous for a number of important reasons. For example, applicantsbelieve, based at least in part on mathematical modeling, that thefluoroolefins of the present invention will not have a substantialnegative affect on atmospheric chemistry, being negligible contributorsto ozone depletion in comparison to some other halogenated species. Thepreferred compositions of the present invention thus have the advantageof not contributing substantially to ozone depletion. The preferredcompositions also do not contribute substantially to global warmingcompared to many of the hydrofluoroalkanes presently in use.

Of course other compounds and/or components that modulate a particularproperty of the compositions (such as cost for example) may also beincluded in the present compositions, and the presence of all suchcompounds and components is within the broad scope of the invention.

In certain preferred forms, compositions of the present invention have aGlobal Warming Potential (GWP) of not greater than about 1500, morepreferably not greater than about 1000, more preferably not greater thanabout 500, and even more preferably not greater than about 150. Incertain embodiments, the GWP of the present compositions is not greaterthan about 100 and even more preferably not greater than about 75. Asused herein, “GWP” is measured relative to that of carbon dioxide andover a 100 year time horizon, as defined in “The Scientific Assessmentof Ozone Depletion, 2002, a report of the World MeteorologicalAssociation's Global Ozone Research and Monitoring Project,” which isincorporated herein by reference.

In certain preferred forms, the present compositions also preferablyhave an Ozone Depletion Potential (ODP) of not greater than 0.05, morepreferably not greater than 0.02 and even more preferably about zero. Asused herein, “ODP” is as defined in “The Scientific Assessment of OzoneDepletion, 2002, A report of the World Meteorological Association'sGlobal Ozone Research and Monitoring Project,” which is incorporatedherein by reference.

The amount of the Formula I compounds (including compounds of Formula IAand Formula II), particularly HFCO-1233 and HFO-1234, and even morepreferably each one of cis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf,HFO-1234yc, HFO-1234zc, HFO-1234ye(E), HFO-1234ye(Z), HFCO-1233xf,cisHFC-1233zd and trans HFCO-1233zd contained in the presentcompositions can vary widely, depending the particular application, andcompositions containing more than trace amounts and less than 100% ofthe compound are within broad the scope of the present invention.Moreover, the compositions of the present invention can be azeotropic,azeotrope-like or non-azeotropic. In preferred embodiments, the presentcompositions, particularly blowing agent and heat transfer compositions,comprise Formula I compounds, preferably HFCO-1233 and HFO-1234 and morepreferably any one or more of cis-HFO-1234ze, trans-HFO-1234ze,HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E), and HFO-1234ye(Z),HFCO-1233xf, cisHFO-1233zd and transHFCO-1233zd in amounts from about 5%by weight to about 99% by weight, and even more preferably from about 5%to about 95%.

Many additional compounds or components, including lubricants,stabilizers, metal passivators, corrosion inhibitors, flammabilitysuppressants, and other compounds and/or components that modulate aparticular property of the compositions (such as cost for example) maybe included in the present compositions, and the presence of all suchcompounds and components is within the broad scope of the invention. Incertain preferred embodiments, the present compositions include, inaddition to the compounds of Formula I (including particularly any oneor more of cis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc,HFO-1234zc, HFO-1234ye(E), and HFO-1234ye(Z) HFO-1234ze and/orHFO-1234yf, HFCO-1233xf, cisHFCO-1233zd and transHFCO-1233zd), one ormore of the following:

-   -   Trichlorofluoromethane (CFC-11)    -   Dichlorodifluoromethane (CFC-12)    -   Difluoromethane (HFC-32)    -   Pentafluoroethane (HFC-125)    -   1,1,2,2-tetrafluoroethane (HFC-134)    -   1,1,1,2-Tetrafluoroethane (HFC-134a)    -   Difluoroethane (HFC-152a)    -   1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)    -   1,1,1,3,3,3-hexafluoropropane (HFC-236fa)    -   1,1,1,3,3-pentafluoropropane (HFC-245fa)    -   1,1,1,3,3-pentafluorobutane (HFC-365mfc)    -   water    -   CO₂

The relative amount of any of the above noted compounds of the presentinvention, as well as any additional components which may be included inpresent compositions, can vary widely within the general broad scope ofthe present invention according to the particular application for thecomposition, and all such relative amounts are considered to be withinthe scope hereof.

Accordingly, applicants have recognized that certain compositions of thepresent invention can be used to great advantage in a number ofapplications. For example, included in the present invention are methodsand compositions relating to heat transfer applications, foam andblowing agent applications, propellant applications, sprayablecomposition applications, sterilization applications, aerosolapplications, compatibilizer application, fragrance and flavorapplications, solvent applications, cleaning applications, inflatingagent applications and others. It is believed that those of skill in theart will be readily able to adapt the present compositions for use inany and all such applications without undue experimentation.

The present compositions are generally useful as replacements for CFCs,such as dichlorodifluormethane (CFC-12), HCFCs, such aschlorodifluoromethane (HCFC-22), HFCs, such as tetrafluoroethane(HFC-134a), and combinations of HFCs and CFCs, such as the combinationof CFC-12 and 1,1-difluorethane (HFC-152a) (the combinationCFC-12:HFC-152a in a 73.8:26.2 mass ratio being known as R-500) inrefrigerant, aerosol, and other applications.

Heat Transfer Compositions

The compositions of the present invention are generally adaptable foruse in heat transfer applications, that is, as a heating and/or coolingmedium, including as evaporative cooling agents.

In connection with evaporative cooling applications, the compositions ofthe present invention are brought in contact, either directly orindirectly, with a body to be cooled and thereafter permitted toevaporate or boil while in such contact, with the preferred result thatthe boiling gas in accordance with the present composition absorbs heatfrom the body to be cooled. In such applications it may be preferred toutilize the compositions of the present invention, preferably in liquidform, by spraying or otherwise applying the liquid to the body to becooled. In other evaporative cooling applications, it may be preferredto permit a liquid composition in accordance with the present intentionto escape from a relatively high pressure container into a relativelylower pressure environment wherein the body to be cooled is in contact,either directly or indirectly, with the container enclosing the liquidcomposition of the present invention, preferably without recovering orrecompressing the escaped gas. One particular application for this typeof embodiment is the self cooling of a beverage, food item, novelty itemor the like. Previous to the invention described herein, priorcompositions, such as HFC-152a and HFC-134a were used for suchapplications. However, such compositions have recently been looked uponnegatively in such application because of the negative environmentalimpact caused by release of these materials into the atmosphere. Forexample, the United States EPA has determined that the use of such priorchemicals in this application is unacceptable due to the high globalwarming nature of these chemicals and the resulting detrimental effecton the environment that may result from their use. The compositions ofthe present invention should have a distinct advantage in this regarddue to their low global warming potential and low ozone depletionpotential, as described herein. Additionally, the present compositionsare expected to also find substantial utility in connection with thecooling of electrical or electronic components, either duringmanufacture or during accelerated lifetime testing. In a acceleratedlifetime testing, the component is sequentially heated and cooled inrapid succession to simulate the use of the component. Such uses wouldtherefore be of particular advantage in the semiconductor and computerboard manufacturing industry. Another advantage of the presentcompositions in this regard is they are expected to exhibit ascontagious electrical properties when used in connection with suchapplications. Another evaporative cooling application comprises methodsfor temporarily causing a discontinuation of the flow of fluid through aconduit. Preferably, such methods would include contacting the conduit,such as a water pipe through which water is flowing, with a liquidcomposition according to the present invention and allowing the liquidcomposition of the present invention to evaporate while in contact withthe conduit so as to freeze liquid contained therein and therebytemporarily stop the flow of fluid through the conduit. Such methodshave distinct advantage in connection with enabling the service or otherwork to be performed on such conduits, or systems connected to suchconduits, at a location downstream of the location at which the presentcomposition is applied.

Although it is contemplated that the compositions of the presentinvention may include the compounds of the present invention in widelyranging amounts, it is generally preferred that refrigerant compositionsof the present invention comprise compound(s) in accordance with FormulaI, more preferably in accordance with Formula IA and/or Formula II, andeven more preferably HFO-1234 (including any one or more ofcis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc,HFO-1234ye(E) and HFO-1234ye(Z)), or HFCO-1233(including any one ofHFCO-1233xf, cisHFCO-1233zd and transHFCO-1233zd) in an amount that isat least about 50% by weight, and even more preferably at least about70% by weight, of the composition.

In certain embodiments, it is preferred that the heat transfercompositions of the present invention comprise transHFO-1234ze, morepreferably at least about 90% by weight transHFO-1234ze, more preferablyat least about 95% by weight transHFO-1234ze, and even more preferablyat least about 99% by weight transHFO-1234ze . In certain preferredembodiments, it is preferred that the heat transfer compositions of thepresent invention comprise at least about 80%, and even more preferablyat least about 90% by weight of HFO-1234, and even more preferably anyone or more of cis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc,HFO-1234zc, HFO-1234ye(E) and HFO-1234ye(Z).

The heat transfer compositions of the present invention comprise incertain embodiments a combination of cisHFO-1234ze and transHFO1234ze.In certain embodiments, the cis:trans weight ratio is not greater than1:99, and even more preferably not greater than 0.1:99. In certainpreferred embodiments, the cis:trans weight ratio of from about 0.1:99to about 10:99, less than is from 1:99 to about 10:99, more preferablyfrom about 1:99 to about 5:95, and even more preferably from about 1:99to about 3:97.

In certain embodiments, it is preferred that the heat transfercompositions of the present invention comprise HFCO-1233zd, morepreferably at least about 90% by weight HFCO-1233zd, more preferably atleast about 95% by weight HFCO-1233zd, and even more preferably at leastabout 99% by weight HFCO-1233zd. In certain preferred embodiments, it ispreferred that the heat transfer compositions of the present inventioncomprise at least about 80%, and even more preferably at least about 90%by weight of HFCO-1233zd, and even more preferably any one or more ofcis-HFCO-1233zd and trans-HFC-1233zd.

The heat transfer compositions of the present invention comprise incertain embodiments a combination of cisHFCO-1233zd and transHFCO1233zd.In certain embodiments, the cis:trans weight ratio is from about 30:70to about 5:95, and even more preferably from about 20:80 to about 5:95,with a ratio of 10:90 being especially preferred in certain embodiments.

The relative amount of the hydrofluoroolefin used in accordance with thepresent invention is preferably selected to produce a heat transferfluid which has the required heat transfer capacity, particularlyrefrigeration capacity, and preferably is at the same timenon-flammable. As used herein, the term non-flammable refers to a fluidwhich is non-flammable in all proportions in air as measured by ASTME-681.

The compositions of the present invention may include other componentsfor the purpose of enhancing or providing certain functionality to thecomposition, or in some cases to reduce the cost of the composition. Forexample, refrigerant compositions according to the present invention,especially those used in vapor compression systems, include a lubricant,generally in amounts of from about 30 to about 50 percent by weight ofthe composition. Furthermore, the present compositions may also includea co-refrigerant, or compatibilzer, such as propane, for the purpose ofaiding compatibility and/or solubility of the lubricant. Suchcompatibilizers, including propane, butanes and pentanes, are preferablypresent in amounts of from about 0.5 to about 5 percent by weight of thecomposition. Combinations of surfactants and solubilizing agents mayalso be added to the present compositions to aid oil solubility, asdisclosed by U.S. Pat. No. 6,516,837, the disclosure of which isincorporated by reference. Commonly used refrigeration lubricants suchas Polyol Esters (POEs) and Poly Alkylene Glycols (PAGs), PAG oils,silicone oil, mineral oil, alkyl benzenes (ABs) and poly(alpha-olefin)(PAO) that are used in refrigeration machinery with hydrofluorocarbon(HFC) refrigerants may be used with the refrigerant compositions of thepresent invention. Commercially available mineral oils include Witco LP250 (registered trademark) from Witco, Zerol 300 (registered trademark)from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 fromCalumet. Commercially available alkyl benzene lubricants include Zerol150 (registered trademark). Commercially available esters includeneopentyl glycol dipelargonate, which is available as Emery 2917(registered trademark) and Hatcol 2370 (registered trademark). Otheruseful esters include phosphate esters, dibasic acid esters, andfluoroesters. In some cases, hydrocarbon based oils are have sufficientsolubility with the refrigerant that is comprised of an iodocarbon, thecombination of the iodocarbon and the hydrocarbon oil might more stablethan other types of lubricant. Such combination may therefore beadvantageous. Preferred lubricants include polyalkylene glycols andesters. Polyalkylene glycols are highly preferred in certain embodimentsbecause they are currently in use in particular applications such asmobile air-conditioning. Of course, different mixtures of differenttypes of lubricants may be used.

In certain preferred embodiments, the heat transfer compositioncomprises from about 10% to about 95% by weight of a compound of FormulaI, more preferably a compound of Formula IA and/or Formula II, and evenmore preferably one or more HFO-1234 compounds, and from about 5% toabout 90% by weight of an adjuvant, particular in certain embodiments aco-refrigerant (such as HFC-152, HFC-125 and/or CF₃I). The use of theterm co-refrigerant is not intended for use herein in a limiting senseregarding the relative performance of the compound of Formula Icompounds, but is used in stead used to identify other components of therefrigerant composition generally that contribute to the desirable heattransfer characteristics of the composition for a desired application.In certain of such embodiments the co-refrigerant comprises, andpreferably consists essentially of, one or more HFCs and/or one or morefluoroiodo C1-C3 compounds, such as trifluroiodomethane, andcombinations of these with each other and with other components.

In preferred embodiments in which the co-refrigerant comprises HFC,preferably HFC-125. the composition comprises HFC in an amount of fromabout 50% by weight to about 95% by weight of the total heat transfercomposition, more preferably from about 60% by weight to about 90% byweight, and even more preferably of from about 70% to about 90% byweight of the composition. In such embodiments the compound of thepresent invention preferably comprises, and even more preferablyconsists essentially of, HFO-1234, HFCO-1233, and combinations of these,and even more preferably any one or more of cis-HFO-1234ze,trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E)HFO-1234ye(Z), cisHFCO-1233zd, and transHFCO-1233zd in an amount of fromabout 5% by weight to about 50% by weight of the total heat transfercomposition, more preferably from about 10% by weight to about 40% byweight, and even more preferably of from about 10% to about 30% byweight of the composition.

In preferred embodiments in which the co-refrigerant comprisesfluoriodocarbon, preferably CF3I, the composition comprisesfluoriodocarbon in an amount of from about 15% by weight to about 50% byweight of the total heat transfer composition, more preferably fromabout 20% by weight to about 40% by weight, and even more preferably offrom about 25% to about 35% by weight of the composition. In suchembodiments the compound of the present invention preferably comprises,and even more preferably consists essentially of, HFO-1234, HFCO-1233,and combinations of these, and even more preferably any one or more ofcis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc,HFO-1234ye(E), HFO-1234ye(Z), cisHFCO-1233zd and transHFCO-1233zd in anamount of from about 50% by weight to about 90% by weight of the totalheat transfer composition, more preferably from about 60% by weight toabout 80% by weight, and even more preferably of from about 65% to about75% by weight of the composition.

The present methods, systems and compositions are thus adaptable for usein connection with a wide variety of heat transfer systems in generaland refrigeration systems in particular, such as air-conditioning(including both stationary and mobile air conditioning systems),refrigeration, heat-pump systems, and the like. In certain preferredembodiments, the compositions of the present invention are used inrefrigeration systems originally designed for use with an HFCrefrigerant, such as, for example, HFC-134a, or an HCFC refrigerant,such as, for example, HCFC-22. The preferred compositions of the presentinvention tend to exhibit many of the desirable characteristics ofHFC-134a and other HFC refrigerants, including a GWP that is as low, orlower than that of conventional HFC refrigerants and a capacity that isas high or higher than such refrigerants and a capacity that issubstantially similar to or substantially matches, and preferably is ashigh as or higher than such refrigerants. In particular, applicants haverecognized that certain preferred embodiments of the presentcompositions tend to exhibit relatively low global warming potentials(“GWPs”), preferably less than about 1000, more preferably less thanabout 500, and even more preferably less than about 150. In addition,the relatively constant boiling nature of certain of the presentcompositions, including the azeotrope-like compositions described in theco-pending patent applications incorporated herein by reference, makesthem even more desirable than certain conventional HFCs, such as R-404Aor combinations of HFC-32, HFC-125 and HFC-134a (the combinationHFC-32:HFC-125:HFC134a in approximate 23:25:52 weight ratio is referredto as R-407C), for use as refrigerants in many applications. Heattransfer compositions of the present invention are particularlypreferred as replacements for HFC-134, HFC-152a, HFC-22, R-12 and R-500.

In certain other preferred embodiments, the present compositions areused in refrigeration systems originally designed for use with aCFC-refrigerant. Preferred refrigeration compositions of the presentinvention may be used in refrigeration systems containing a lubricantused conventionally with CFC-refrigerants, such as mineral oils,polyalkylbenzene, polyalkylene glycol oils, and the like, or may be usedwith other lubricants traditionally used with HFC refrigerants. As usedherein the term “refrigeration system” refers generally to any system orapparatus, or any part or portion of such a system or apparatus, whichemploys a refrigerant to provide cooling. Such refrigeration systemsinclude, for example, air conditioners, electric refrigerators, chillers(including chillers using centrifugal compressors), transportrefrigeration systems, commercial refrigeration systems and the like.

Many existing refrigeration systems are currently adapted for use inconnection with existing refrigerants, and the compositions of thepresent invention are believed to be adaptable for use in many of suchsystems, either with or without system modification. Many applicationsthe compositions of the present invention may provide an advantage as areplacement in smaller systems currently based on certain refrigerants,for example those requiring a small refrigerating capacity and therebydictating a need for relatively small compressor displacements.Furthermore, in embodiments where it is desired to use a lower capacityrefrigerant composition of the present invention, for reasons ofefficiency for example, to replace a refrigerant of higher capacity,such embodiments of the present compositions provide a potentialadvantage. Thus, it is preferred in certain embodiments to usecompositions of the present invention, particularly compositionscomprising a substantial proportion of, and in some embodimentsconsisting essentially of the present compositions, as a replacement forexisting refrigerants, such as : HFC-134a; CFC-12; HCFC-22; HFC-152a;combinations of pentfluoroethane (HFC-125), trifluorethane (HFC-143a)and tetrafluoroethane (HFC-134a) (the combinationHFC-125:HFC-143a:HFC134a in approximate 44:52:4 weight ratio is referredto as R-404A); combinations of HFC-32, HFC-125 and HFC-134a (thecombination HFC-32:HFC-125:HFC134a in approximate 23:25:52 weight ratiois referred to as R-407C); combinations of methylene fluoride (HFC-32)and pentfluoroethane (HFC-125) (the combination HFC-32:HFC-125 inapproximate 50:50 weight ratio is referred to as R-410A); thecombination of CFC-12 and 1,1-difluorethane (HFC-152a) (the combinationCFC-12:HFC-152a in a 73.8:26.2 weight ratio is referred to R-500); andcombinations of HFC-125 and HFC-143a (the combination HFC-125:HFC143a inapproximate 50:50 weight ratio is referred to as R-507A). In certainembodiments it may also be beneficial to use the present compositions inconnection with the replacement of refrigerants formed from thecombination HFC-32:HFC-125:HFC134a in approximate 20:40:40 weight ratio,which is referred to as R-407A, or in approximate 15:15:70 weight ratio,which is referred to as R-407D. The present compositions are alsobelieved to be suitable as replacements for the above noted compositionsin other applications, such as aerosols, blowing agents and the like, asexplained elsewhere herein.

In certain applications, the refrigerants of the present inventionpotentially permit the beneficial use of larger displacementcompressors, thereby resulting in better energy efficiency than otherrefrigerants, such as HFC-134a. Therefore the refrigerant compositionsof the present invention provide the possibility of achieving acompetitive advantage on an energy basis for refrigerant replacementapplications, including automotive air conditioning systems and devices,commercial refrigeration systems and devices, chillers, residentialrefrigerator and freezers, general air conditioning systems, heat pumpsand the like.

Many existing refrigeration systems are currently adapted for use inconnection with existing refrigerants, and the compositions of thepresent invention are believed to be adaptable for use in many of suchsystems, either with or without system modification. In manyapplications the compositions of the present invention may provide anadvantage as a replacement in systems which are currently based onrefrigerants having a relatively high capacity. Furthermore, inembodiments where it is desired to use a lower capacity refrigerantcomposition of the present invention, for reasons of cost for example,to replace a refrigerant of higher capacity, such embodiments of thepresent compositions provide a potential advantage. Thus, It ispreferred in certain embodiments to use compositions of the presentinvention, particularly compositions comprising a substantial proportionof, and in some embodiments consisting essentially of, HFO-1234(preferably any one or more of cis-HFO-1234ze, trans-HFO-1234ze,HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E) and HFO-1234ye(Z)) asa replacement for existing refrigerants, such as HFC-134a. In certainapplications, the refrigerants of the present invention potentiallypermit the beneficial use of larger displacement compressors, therebyresulting in better energy efficiency than other refrigerants, such asHFC-134a. Therefore the refrigerant compositions of the presentinvention, particularly compositions comprising any one or more ofcis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc,HFO-1234ye(E) and HFO-1234ye(Z), provide the possibility of achieving acompetitive advantage on an energy basis for refrigerant replacementapplications.

It is contemplated that the compositions of the present, includingparticularly those which comprise any one or more of cis-HFO-1234ze,trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E)HFO-1234ye(Z), cisHFCO-1233zd and transHFCO-1233zd also have advantage(either in original systems or when used as a replacement forrefrigerants such as CFC-11, CFC-12, HCFC-22, HFC-134a, HFC-152a, R-500and R-507A), in chillers typically used in connection with commercialair conditioning systems. In certain of such embodiments it is preferredto include in the present compositions, particularly those comprisingHFO-1234yf and/or HFO-1234ze, from about 0.5 to about 30% of asupplemental flammability suppressant, and in certain cases morepreferably 0.5% to about 15% by weight and even more preferably fromabout 0.5 to about 10% on a weight basis. In this regard it is notedthat the certain of HFO-1234 and/or HFO-1225 components of the presentcompositions may in certain embodiments act as flammability suppressantswith respect to other components in the composition. Thus, componentsother than HFO-1234 and HFO-1225 which have flammability suppressantfunctionality in the composition will sometimes be referred to herein asa supplemental flammability suppressant.

In certain preferred embodiments, the present compositions include, inaddition to the compounds of Formula I (including particularly HFO-1234(including any one or more of cis-HFO-1234ze, trans-HFO-1234ze,HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E) and HFO-1234ye(Z)),and HFCO-1233 (including particularly cisHFCO-1233zd andtransHFCO-1233zd), one or more of the following additional compoundsthat may be included primarily for their impact on the heat transfercharacteristics, cost and the like. The following components may thus beincluded in the compositions as co-heat transfer fluids (orco-refrigerants in the case of cooling operations):

-   -   Trichlorofluoromethane (CFC-11)    -   Dichlorodifluoromethane (CFC-12)    -   Difluoromethane (HFC-32)    -   Pentafluoroethane (HFC-125)    -   1,1,2,2-tetrafluoroethane (HFC-134)    -   1,1,1,2-Tetrafluoroethane (HFC-134a)    -   Difluoroethane (HFC-152a)    -   1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)    -   1,1,1,3,3,3-hexafluoropropane (HFC-236fa)    -   1,1,1,3,3-pentafluoropropane (HFC-245fa)    -   1,1,1,3,3-pentafluorobutane (HFC-365mfc)    -   water    -   CO₂

Blowing Agents, Foams and Foamable Compositions

Blowing agents may also comprise or constitute one or more of thepresent compositions. As mentioned above, the compositions of thepresent invention may include the compounds of the present invention inwidely ranging amounts. It is generally preferred, however, that forpreferred compositions for use as blowing agents in accordance with thepresent invention, compound(s) in accordance with Formula I, and evenmore preferably Formula IA and/or Formula II, are present in an amountthat is at least about 5% by weight, and even more preferably at leastabout 15% by weight, of the composition. In certain preferredembodiments, the blowing agent comprises at least about 50% by weight ofthe present compositions, and in certain embodiments the blowing agentconsists essentially of the present compositions. In certain preferredembodiments, the blowing agent compositions of the present invention andinclude, in addition to the compounds of Formula I, including HFO-1234(preferably any one or more of cis-HFO-1234ze, trans-HFO-1234ze,HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E) and HFO-1234ye(Z)) andHFCO-1233 (prefereably any one or more of cisHFCO-1233zd andtransHFCO-1233zd), one or more of co-blowing agents, fillers, vaporpressure modifiers, flame suppressants, stabilizers and like adjuvants.The co-blowing agent in accordance with the present invention cancomprise a physical blowing agent, a chemical blowing agent (whichpreferably in certain embodiments comprises water) or a blowing agenthaving a combination of physical and chemical blowing agent properties.It will also be appreciated that the blowing agents included in thepresent compositions, including the compounds of Formula I as well asthe co-blowing agent, may exhibit properties in addition to thoserequired to be characterized as a blowing agent. For example, it iscontemplated that the blowing agent compositions of the presentinvention may include components, including the compounds or Formula Idescribed above, which also impart some beneficial property to theblowing agent composition or to the foamable composition to which it isadded. For example, it is within the scope of the present invention forthe compound of Formula I or for the co-blowing agent to also act as apolymer modifier or as a viscosity reduction modifier.

By way of example, one or more of the following components may beincluded in certain preferred blowing agents of the present invention inwidely varying amounts: hydrocarbons, hydrofluorocarbons (HFCs), ethers,alcohols, aldehydes, ketones, methyl formate, formic acid, water,trans-1,2-dichloroethylene, carbon dioxide and combinations of any twoor more of these. Among ethers, it is preferred in certain embodimentsto use ethers having from one to six carbon atoms. Among alcohols, it ispreferred in certain embodiments to use alcohols having from one to fourcarbon atoms. Among aldehydes, it is preferred in certain embodiments touse aldehydes having from one to four carbon atoms.

1. The Ethers

In certain preferred embodiments, present compositions, particularlyblowing agent compositions, include at least one ether, preferably whichfunctions as a co-blowing agent in the composition. The ether(s) used inaccordance with this aspect of the invention comprise fluorinated ethers(FEs), more preferably one or more hydro-fluorinated ethers (HFEs)), andeven more preferably one or more C3 to C5 hydro-fluorinated ethers inaccordance with Formula (III) below:C_(a)H_(b)F_(c)—O—C_(d)H_(e)F_(f)  (III)

where

-   -   a=1-6, more preferably 2-5, and even more preferably 3-5,    -   b=1-12, more preferably 1-6, and even more preferably 3-6,    -   c=1-12, more preferably 1-6, and even more preferably 2-6,    -   d=1-2    -   e=0-5, more preferably 1-3    -   f=0-5, more preferably 0-2,    -   and where one of said C_(a) may be bound to one of said C_(d) to        form a cyclofluoroether.

Certain preferred embodiments of the present invention are directed tocompositions comprising at least one fluoroalkene as described herein,preferably in certain embodiments chlorofluoroalkenes such asHFCO-1233xd, and at least one fluoro-ether, more preferably at least onehydro-fluoroether, containing from 2 to 8, preferably 2 to 7, and evenmore preferably 2 to 6 carbon atoms, and in certain embodiments mostpreferably three carbon atoms. The hydro-fluoroether compounds of thepresent invention are sometimes referred to herein for the purpose ofconvenience as hydrofluoro-ethers or “HFEs” if they contain at least onehydrogen.

Applicants believe that, in general, the fluoroethers in accordance withthe present disclosure and in particular in accordance with aboveidentified Formula (III) are generally effective and exhibit utility incombination with the fluoroalkene compounds in accordance with theteachings contained herein. However, applicants have found that fromamong the fluroethers, it is preferred to use in certain embodiments,especially embodiments relating to blowing agent compositions and foamand foaming methods, to utilize hydrofluorethers that are at leastdifluorinated, more preferbably at least trifluorinated, and even morepreferably at least tetra-fluorinated. Especially preferred in certainembodiments are tetrafluorinated fluorethers having from 3 to 5 carbonatoms, more preferably 3 to 4 carbon atoms, and even more preferably 3carbon atoms.

In certain preferred embodiments, the ether compound of the presentinvention comprises a 1,1,2,2-tetrafluoroethylmethylether (which issometimes referred to herein as HFE-245pc or HFE-245cb2), including anyand all isomeric forms thereof.

The amount of the Formula III compounds, particularly1,1,2,2-tetrafluoroethylmethylether contained in the presentcompositions can vary widely, depending the particular application, andcompositions containing more than trace amounts and less than 100% ofthe compound are within broad the scope of the present invention. Inpreferred embodiments, the present compositions, particularly blowingagent compositions, comprise Formula III compounds, including preferredgroups of compounds, in amounts from about 1% by weight to about 99% byweight, more preferably from about 5% to about 95% by weight, and evenmore preferably from 40% to about 90% by weight.

One or more of following compounds are preferred for use in accordancewith certain preferred embodiments of the present invention:

-   -   CHF₂OCH₂F (HFE-143E)    -   CH₂FOCH₂F (HFE-152E)    -   CH₂FOCH₃ (HFE-161E)    -   cyclo-CF₂CH₂OCF₂O (HFE-c234fEαβ)    -   cyclo-CF₂CF₂CH₂O (HFE-c234fEβγ)    -   CHF₂OCF₂CHF₂ (HFE-236caE)    -   CF₃CF₂OCH₂F (HFE-236cbEβγ)    -   CF₃OCHFCHF₂ (HFE-236eaEαβ)    -   CHF₂OCHFCF₃ (HFE-236eaEβγ)    -   CHF₂OCF₂CH₂F (HFE-245caEαβ)    -   CH₂FOCF₂CHF₂ (HFE-245caEβγ)    -   CF₃OCF₂CH₃ (HFE-245cbEβγ)    -   CHF₂CHFOCHF₂ (HFE-245eaE)    -   CF₃OCHFCH₂F (HFE-245ebEαβ)    -   CF₃CHFOCH₂F (HFE-245ebEβγ)    -   CF₃OCH₂CF₂H (HFE-245faEαβ)    -   CHF₂OCH₂CF₃ (HFE-245faEβγ)    -   CH₂FCF₂OCH₂F (HFE-254caE)    -   CHF₂OCF₂CH₃ (HFE-254cbEαβ)    -   CHF₂CF₂OCH₃ (HFE-254caEβγ)    -   CH₂FOCHFCH₂F(HFE-254eaEαβ)    -   CF₃OCHFCH₃ (HFE-254ebEαβ)    -   CF₃CHFOCH₃ (HFE-254ebEβγ)    -   CHF₂OCH₂CHF₂ (HFE-254faE)    -   CF₃OCH₂CH₂F (HFE-254fbEαβ)    -   CF₃CH₂OCH₂F(HFE-254fbEβγ)    -   CH₃OCF₂CH₂F(HFE-263caEβγ)    -   CF₃CH₂OCH₃(HFE-263fbEβγ)    -   CH₃OCH₂CHF₂ (HFE-272fbEβγ)    -   CHF₂OCHFCF₂CF₃ (HFE-338mceEγδ)    -   CHF₂OCF₂CHFCF₃ (HFE-338mceEγδ)_(—)    -   CF₃CF₂OCH₂CF₃ (HFE-338mfEβγ)    -   (CF₃)₂CHOCHF₂ (HFE-338mmzEβγ)    -   CF₃CF₂CF₂OCH₃ (HFE-347sEγδ)    -   CHF₂OCH₂CF₂CF₃ (HFE-347mfcEγδ)    -   CF₃OCH₂CF₂CHF₂ (HFE-347mfcEαβ)    -   CH₃OCF₂CHFCF₃ (HFE-356mecEγδ)    -   CH₃OCH(CF₃)₂ (HFE-356mmzEβγ)    -   CF₃CF₂OCH₂CH₃(HFE-365mcEβγ)    -   CF₃CF₂CH₂OCH₃(HFE-365mcEγδ)    -   CF₃CF₂CF₂OCHFCF₃ (HFE-42-11meEγδ)    -   CF₃CFCF₃CF₂OCH₃    -   CF₃CF₂CF₂CF₂OCH₃    -   CF₃CFCF₃CF₂OCH₂CH₃    -   CF₃CF₂CF₂CF₂OCH₂CH₃    -   CF₃CF₂CF₂OCH₃.

It should be understood that the present inventors contemplate that anytwo or more of the above noted HFEs, may be used in combination inaccordance with preferred aspects of the present invention. For example,it is contemplated that a material sold under the trade name HFE-7100 by3M, which is understood to be a mixture of from about 20% to about 80%of methyl nonafluoroisobutyl ether and from about 20% to about 80%methyl nonafluorobutyl ether, may be used to advantage in accordancewith certain preferred embodiments of the present invention. By way offurther example, it is contemplated that a material sold under the tradename HFE-7200 by 3M, which is understood to be a mixture of from about20% to about 80% of ethyl nonafluoroisobutyl ether and from about 20% toabout 80% ethyl nonafluorobutyl ether, may be used to advantage inaccordance with certain preferred embodiments of the present invention.

It is also contemplated that any one or more of the above-listed HFEsmay be used in combination with other compounds as well, including otherHFEs not specifically listed herein and/or other compounds with whichthe designated fluoroether is known to form an azeotrope. For example,each of the following compounds is known to form an azeotrope withtrans-dichloroethylene, and it is contemplated that for the purposes ofthe present invention the use of such azeotropes should be considered tobe within the broad scope of the invention:

-   -   CF₃CFCF₃CF₂OCH₃    -   CF₃CF₂CF₂CF₂OCH₃    -   CF₃CFCF₃CF₂OCH₂CH₃    -   CF₃CF₂CF₂CF₂OCH₂CH₃    -   CF₃CF₂CF₂OCH₃.

2. The Hydrofluorocarbons

In certain embodiments it is preferred that the compositions of thepresent invention, including particularly the blowing agent compositionsof the present invention, include one or more HFCs as co-blowing agents,more preferably one or more C1-C4 HFCs. For example, the present blowingagent compositions may include one or more of difluoromethane (HFC-32),fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane(HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125),pentafluoropropane (HFC-245), hexafluoropropane (HFC-236),heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365),hexafluorobutane (HFC-356) and all isomers of all such HFC's.

In certain embodiments, one or more of the following HFC isomers arepreferred for use as co-blowing agents in the compositions of thepresent invention:

-   -   fluoroethane (HFC-161)    -   1,1,1,2,2-pentafluoroethane (HFC-125)    -   1,1,2,2-tetrafluoroethane (HFC-134)    -   1,1,1,2-tetrafluoroethane (HFC-134a)    -   1,1,1-trifluoroethane (HFC-143a)    -   1,1-difluoroethane (HFC-152a)    -   1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea)    -   1,1,1,3,3,3-hexafluoropropane (HFC-236fa)    -   1,1,1,2,3,3-hexafluoropropane (HFC-236ea)    -   1,1,1,2,3-pentafluoropropane (HFC-245eb)    -   1,1,2,2,3-pentafluoropropane (HFC-245ca)    -   1,1,1,3,3-pentafluoropropane (HFC-245fa)    -   1,1,1,3,3-pentafluorobutane (HFC-365mfc) and    -   1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-43-10-mee).

3. The Hydrocarbons

In certain embodiments it is preferred that the compositions of thepresent invention, including particularly the blowing agent compositionsof the present invention include one or more hydrocarbons, morepreferably C3-C6 hydrocarbons. The present blowing agent compositionsmay include in certain preferred embodiments, for example: propane; iso-and normal-butane (each of such butanes being preferred for use as ablowing agent for thermoplastic foams); iso-, normal-, neo- and/orcyclo-pentane (each of such pentanes being preferable for use as ablowing agent for thermoset foams); iso- and normal-hexane; andheptanes.

Certain preferred embodiments of the present compositions, includingparticularly the blowing agent compositions, comprise one or moremonochlorotrifluorpropenes, particularly HFCO-1233zd, and at least onehydrocarbon selected from the group consisting of iso-pentane,normal-pentane, cyclo-pentane, and combinations of these, withcombinations comprising from about 50% to about 85% by weight ofcyclo-pentane, and even more preferably from about 65% to about 75% byweight of cyclo-pentane, being preferred.

4. The Alcohols

In certain embodiments it is preferred that the compositions of thepresent invention, including particularly the blowing agent compositionsof the present invention, include one or more alcohols, preferably oneor more C1-C4 alcohols. For example, the present blowing agentcompositions may include one or more of methanol, ethanol, propanol,isopropanol, butanol, iosbutanol, t-butanol, and octanols. From amongthe octanols, isooctanol (ie., 2-ethyl-1-hexanol) is preferred for usein blowing agent formulations and in solvent compositons

Certain preferred embodiments of the present compositions, includingparticularly the blowing agent compositions, comprise one or moremonochlorotrifluorpropenes, particularly HFCO-1233zd, and at least onealcohol selected from the group consisting of methanol, ethanol,propanol, isopropanol, butanol, iosbutanol, t-butanol and combinationsof these.

5. The Aldehydes

In certain embodiments it is preferred that the compositions of thepresent invention, including particularly the blowing agent compositionsof the present invention include one or more aldehydes, particularlyC1-C4 aldehydes, including formaldehyde, acetaldehyde, propanal, butanaland isobutanal.

6. The Ketones

In certain embodiments it is preferred that the compositions of thepresent invention, including particularly the blowing agentcompositions, the aerosol and the solvent compositions of the presentinvention include one or more ketones, preferably C1-C4 ketones. Forexample, the present blowing agent compositions may include one or moreof acetone, methylethylketone, and methylisobutylketone.

7. The Chlorocarbons

In certain embodiments it is preferred that compositions of the presentinvention, including particularly the blowing agent compositions of thepresent invention include one or more chlorocarbons, more preferablyC1-C3 chlorocarbons. The present compositions may include in certainpreferred embodiments, for example: 1-chloropropane; 2-chloropropane;trichloroethylene; perchloroethylene; methene chloride; trans-1,2dicchloroethylenes, and combinations of these, with trans-1,2dicchloroethylenes being especially preferred in certain embodiments,particularly blowing agent embodiments.

8. Other Compounds

In certain embodiments it is preferred that compositions of the presentinvention, including particularly the blowing agent compositions of thepresent invention include one or more additional compounds, includingwater, CO₂, methylformate, formic acid, dimethoxymethane (DME) andcombinations of these. From among the above, DME is particularlypreferred for use in blowing agent compositions and as a propellant inaerosol compositions in accordance with the present invention,particularly in combination with HFCO-1233zd. From among the above,water and CO₂ are particularly preferred for use in blowing agents andas a propellant in accordance with the present invention, particularlyin combination with HFCO-1233zd.

The relative amount of any of the above noted additional compounds,which are contemplated for use in certain embodiments as co-blowingagents, as well as any additional components which may be included inpresent compositions, can vary widely within the general broad scope ofthe present invention according to the particular application for thecomposition, and all such relative amounts are considered to be withinthe scope hereof. Applicants note, however, that one particularadvantage of at least certain of the compounds of Formula I inaccordance with the present invention, for example HFO-1234ze and,HCFO-1233zd, is the relatively low flammability and relatively lowtoxicity of such compounds. Accordingly, in certain embodiments it ispreferred that the blowing agent composition of the present inventioncomprise at least one co-blowing agent and an amount of compound(s) inaccordance with Formula I sufficient to produce a blowing agentcomposition which is overall nonflammable. Thus, in such embodiments,the relative amounts of the co-blowing agent in comparison to thecompound of Formula I will depend, at least in part, upon theflammability of the co-blowing agent.

The blowing agent compositions of the present invention may include thecompounds of the present invention in widely ranging amounts. It isgenerally preferred, however, that for preferred compositions for use asblowing agents in accordance with the present invention, compound(s) inaccordance with Formula I, and even more preferably Formula II, arepresent in an amount that is at least about 1% by weight, morepreferably at least about 5% by weight, and even more preferably atleast about 15% by weight, of the composition. In certain preferredembodiments, the blowing agent comprises at least about 50% by weight ofthe present blowing agent compound(s), and in certain embodiments theblowing agent consists essentially of compounds in accordance with thepresent invention. In this regard it is noted that the use of one ormore co-blowing agents is consistent with the novel and basic featuresof the present invention. For example, it is contemplated that waterwill be used as either a co-blowing or in combination with otherco-blowing agents (such as, for example, pentane, particularlycyclopentane) in a large number of embodiments.

It is contemplated that the blowing agent compositions of the presentinvention may comprise, preferably in amounts of at least about 15% byweight of the composition of one or more HFO-1234 and/or HFCO-1233zd,including particularly cis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf,HFO-1234yc, HFO-1234zc, HFO-1234ye(E), HFO-1234ye(Z), trans-HFCO-1233zdand cis-HFCO-1233zd or combinations of two or more of these. In manypreferred embodiments, a co-blowing agent comprising water is includedin the compositions, most preferably in compositions directed to the useof thermosetting foams.

In certain preferred embodiments, the blowing agent compositions of thepresent invention comprise a combination of cisHFO-1234ze andtransHFO1234ze in a cis:trans weight ratio of from about 1:99 to about50:50, more preferably from about 10:90 to about 30:70. In certainembodiments, it may be preferred to use a combination of cisHFO-1234zeand transHFO1234ze in a cis:trans weight ratio of from about 1:99 toabout 10:90, and preferably from about 1:99 to about 5:95. Of course, itmay be desirable in certain embodiments to use combinations in which thecis-isomer is present in a higher concentration than the trans-isomer,as may be the case, for example, for use with foamable compositionsadapted for use with liquid blowing agents.

In certain embodiments, it is preferred that the blowing agentcompositions of the present invention comprise HFCO-1233zd, morepreferably at least about 90% by weight HFCO-1233zd, more preferably atleast about 95% by weight HFCO-1233zd, and even more preferably at leastabout 99% by weight HFCO-1233zd. In certain preferred embodiments, it ispreferred that the blowing agent compositions of the present inventioncomprise at least about 80%, and even more preferably at least about 90%by weight of HFCO-1233zd, and even more preferably any one or more ofcis-HFCO-1233zd and trans-HFC-1233zd.

The blowing agent compositions of the present invention comprise incertain embodiments a combination of cisHFCO-1233zd and transHFCO1233zd.In certain embodiments, the cis:trans weight ratio is from about 30:70to about 5:95, and even more preferably from about 20:80 to about 5:95,with a ration of 10:90 being especially preferred in certainembodiments.

In certain preferred embodiments, the blowing agent compositioncomprises from about 30% to about 95% by weight, more preferably fromabout 30% to about 96%, more preferably from about 30% to about 97%, andeven more preferably from about 30% to about 98% by weight, and evenmore preferably from about 30% to about 99% by weight of a compound ofFormula I, more preferably a compound of Formula II, and even morepreferably one or more HFO-1234 and/or HFCO-1233 (including particularlycisHFCO-1233zd, transHFCO-1233zd, and all combinations of these), andfrom about 5% to about 90% by weight, more preferably from about 5% toabout 65% by weight of co-blowing agent, including one or morefluoroethers. In certain of such embodiments the co-blowing agentcomprises, and preferably consists essentially of a compound selectedfrom the group consisting of , H₂O, HCs, HEs, HFCs, HFEs, hydrocarbons,alcohols (preferably C2, C3 and/or C4 alcohols), ketones, CO₂, andcombinations of any two or more of these.

In other embodiments, the invention provides foamable compositions. Thefoamable compositions of the present invention generally include one ormore components capable of forming foam having. In certain embodiments,the one or more components comprise a thermosetting composition capableof forming foam and/or foamable compositions. Examples of thermosettingcompositions include polyurethane and polyisocyanurate foamcompositions, and also phenolic foam compositions. With respect to foamtypes, particularly polyurethane foam compositions, the presentinvention provides rigid foam (both closed cell, open cell and anycombination thereof), flexible foam, and semiflexible foam, includingintegral skin foams. The present invention provides also singlecomponent foams, which include sprayable single component foams.

The reaction and foaming process may be enhanced through the use ofvarious additives such as catalysts and surfactant materials that serveto control and adjust cell size and to stabilize the foam structureduring formation. Furthermore, it is contemplated that any one or moreof the additional components described above with respect to the blowingagent compositions of the present invention could be incorporated intothe foamable composition of the present invention. In such thermosettingfoam embodiments, one or more of the present compositions are includedas or part of a blowing agent in a foamable composition, or as a part ofa two or more part foamable composition, which preferably includes oneor more of the components capable of reacting and/or foaming under theproper conditions to form a foam or cellular structure.

In certain other embodiments, the one or more components comprisethermoplastic materials, particularly thermoplastic polymers and/orresins. Examples of thermoplastic foam components include polyolefins,such as for example monovinyl aromatic compounds of the formula Ar—CHCH2wherein Ar is an aromatic hydrocarbon radical of the benzene series suchas polystyrene (PS),(PS). Other examples of suitable polyolefin resinsin accordance with the invention include the various ethylene resinsincluding the ethylene homopolymers such as polyethylene (PE), andethylene copolymers, polypropylene (PP) and polyethyleneterepthalate(PET), and foams formed there from, preferably low-density foams. Incertain embodiments, the thermoplastic foamable composition is anextrudable composition.

The invention also relates to foam, and preferably closed cell foam,prepared from a polymer foam formulation containing a blowing agentcomprising the compositions of the invention. In yet other embodiments,the invention provides foamable compositions comprising thermoplastic orpolyolefin foams, such as polystyrene (PS), polyethylene (PE),polypropylene (PP) and polyethyleneterpthalate (PET) foams, preferablylow-density foams.

Specific Preferred Compositions

A. Compositions Containing 1,1,1-trifluoro, 3-chloropropene (HFO-1233zd)

Applicants have developed several compositions which include as anessential component trifluoromonochloropropene, preferably CF₃CH═CHCl(HFO-1233zd), and at least one additional compound. In suchcompositions, the amount of the HFO-1233zd may vary widely, including inall cases constituting the balance of the composition after all othercomponents in composition are accounted for. In certain preferredembodiments, the amount of trifluoromonochloropropene, preferably eachof transHFCO-1233zd, cisHFCO-1233zd and combinations of these, in thecomposition can be in accordance with the following ranges: from about 1wt % to about 99 wt %; from about 80 wt % to about 99 wt %; from about 1wt % to about 20 wt %; from about 1 wt % to about 25 wt %; from about 1wt % to about 30 wt %; and from about 1 wt % to about 50 wt %. Preferredcompositions of this type are described in the Table below, with allpercentages being in percent by weight and being understood to beproceeded by the word “about” in connection with the additional compoundspecified in the table. In additional, it will be understood that theTable below applies to each of trans-HFCO-1233zd, cisHFCO-1233zd and allcombinations and proportions of these two compounds.

COMBINATIONS WITH HFCO-1233zd* Second Third Preferred PreferredPreferred ADDITIONAL COMPOUND Range Range Range HFOS Chlorofluorobutenes1 to 99 1 to 20 80 to 99 Tetrafluorobutene 1 to 99 1 to 20 80 to 99Pentafluorobutene 1 to 99 1 to 20 80 to 99 HFO-1354 1 to 99 1 to 20 80to 99 HFO-1345 1 to 99 1 to 20 80 to 99 trans-HFO-1234ze 1 to 99 1 to 2080 to 99 cis-HFO1234ze 1 to 99 1 to 20 80 to 99 HFO-1234yf 1 to 99 1 to20 80 to 99 HFO1225yc 1 to 99 1 to 50 na CF3CH═CHCF3 (E & Z) 1 to 99 1to 50 na (CF3)2CFCH═CHF (E & Z) 1 to 99 1 to 50 2a (CF3)2CFCH═CF2 1 to99 1 to 50 na CF3CHFC═CHF (E & Z) 1 to 99 1 to 50 na (C2F5)(CF3)C═CH2 1to 99 1 to 50 na Trifluoropropene (all isomers) 1 to 99 1 to 50 na(C2F5)(CF3)C═CH2 1 to 99 1 to 50 na transCHF═CFCHF2 (HFO- 1 to 99 1 to20 80 to 99 1234yeZ) cisCHF═CFCHF2 (HFO- 1 to 99 1 to 20 80 to 991234yeE) HFCs HFC-245fa 1 to 99 1 to 70 na HFC-245eb 1 to 99 1 to 70 naHFC-245ca 1 to 99 1 to 70 na HFC-227ea 1 to 99 1 to 70 na HFC-236ea 1 to99 1 to 70 na HFC-236fa 1 to 99 1 to 70 na HFC-134a 1 to 99 1 to 70 naHFC-134 1 to 99 1 to 70 na HFC-152a 1 to 99 1 to 70 na HFC-32 1 to 99 1to 70 na HFC-125 1 to 99 1 to 70 na HFC-143a 1 to 99 1 to 70 naHFC-365mfc 1 to 99 1 to 70 na HFC-161 1 to 99 1 to 70 na HFC-43-10mee 1to 99 1 to 70 na HFEs CHF2—O—CHF2 1 to 99 na na CHF2—O—CH2F 1 to 99 nana CH2F—O—CH2F 1 to 99 na na CH2F—O—CH3 1 to 99 na naCYCLO-CF2—CH2—CF2—O 1 to 99 na na CYCLO-CF2—CF2—CH2—O 1 to 99 na naCHF2—O—CF2—CHF2 1 to 99 na na CF3—CF2—O—CH2F 1 to 99 na naCHF2—O—CHF—CF3 1 to 99 na na CHF2—O—CF2—CHF2 1 to 99 na naCH2F—O—CF2—CHF2 1 to 99 na na CF3—O—CF2—CH3 1 to 99 na naCHF2—CHF—O—CHF2 1 to 99 na na CF3—O—CHF—CH2F 1 to 99 na naCF3—CHF—O—CH2F 1 to 99 na na CF3—O—CH2—CHF2 1 to 99 na na CHF2—O—CH2—CF31 to 99 na na CH2F—CF2—O—CH2F 1 to 99 na na CHF2—O—CF2—CH3 1 to 99 na naCHF2—CF2—O—CH3 (254pc) 1 to 99 na na CH2F—O—CHF—CH2F 1 to 99 na naCHF2—CHF—O—CH2F 1 to 99 na na CF3—O—CHF—CH3 1 to 99 na na CF3—CHF—O—CH31 to 99 na na CHF2—O—CH2—CHF2 1 to 99 na na CF3—O—CH2—CH2F 1 to 99 na naCF3—CH2—O—CH2F 1 to 99 na na CF2H—CF2—CF2—O—CH3 1 to 99 na naHydrocarbons 1 to 99 na Propane 1 to 99 na na Butane 1 to 99 na naIsobutane 1 to 99 na na n-pentane (high HFO) 1 to 99 na na n-pentane(high n-pentane) 1 to 99 na na Isopentane (High HFO) 1 to 99 na naIsopentane (High isopentane) 1 to 99 na na Neopentane (High HFO) 1 to 99na na Neopentane (High 1 to 99 na na neopentane) Cyclopentane (High HFO)1 to 99 na na Cyclopentane (High 1 to 99 na na cyclopentane) n-hexane 1to 99 na na Isohexane 1 to 99 na na Heptane 1 to 99 na na AlcoholsMethanol 1 to 50 1 to 20 na Ethanol 1 to 50 1 to 20 na Proponal 1 to 501 to 20 na Isopropanol 1 to 50 1 to 20 na Butanol 1 to 50 1 to 20 naIsobutanol 1 to 50 1 to 20 na t-butanol 1 to 50 1 to 20 na EthersDimethylether 1 to 50 na na Methylethylether 1 to 50 1 to 30 na diethylether 1 to 50 Na Na Methylpropylether 1 to 50 1 to 30 namethylisopropylether 1 to 50 1 to 30 na Ethylpropylether 1 to 50 1 to 30na Ethylisopropylether 1 to 50 1 to 30 na Dipropylether 1 to 50 1 to 30na Diisopropylether 1 to 50 1 to 30 na dimethyloxymethane 1 to 50 1 to30 na Diethoxymethane 1 to 50 1 to 30 na Dipropoxymethane 1 to 50 1 to30 na Dibutoxymethane 1 to 50 1 to 30 na Aldehydes Formaldehyde 1 to 9910 to 90  10 to 80 Acetaldehyde 1 to 99 10 to 90  10 to 80 Propanal 1 to99 10 to 90  10 to 80 Butanal 1 to 99 10 to 90  10 to 80 Isobutanal 1 to99 10 to 90  10 to 80 Ketones Acetone 1 to 50 1 to 30 naMethylethylketone 1 to 50 1 to 30 na Methylisobutylketone 1 to 50 1 to30 na Others methyl formate 1 to 99 10 to 90  10 to 80 formic acid 1 to99 10 to 90  10 to 80 Water 1 to 99 1 to 50  1 to 30 trans-1,2dichloroethylene 1 to 99 1 to 50  1 to 30 Carbon dioxide 1 to 99 10 to90  10 to 80 cis-HFO-1234ze + HFO- 1 to 25/1 to Na Na 1225yez 50 All theabove plus water All the above plus CO2 All the above plus trans 1,2-dichloroethylene All the above plus methyl formate cis-HFO-1234ze + CO2cis-HFO-1234ze + HFO- 1225yez + CO2 cis-HFO-1234ze + HFC-245fa 1 to 25/1to 1 to 20/1 to 1 to 15/1 to 50 25 10 * - Each combination is understoodto be with either cisHFCO-1233zd, transHFCO-1233zd, and all combinationsof cis and trans.

In preferred embodiments in which the co-blowing agent comprises H₂O,the composition comprises H₂O in an amount of from about 5% by weight toabout 50% by weight of the total blowing agent composition, morepreferably from about 10% by weight to about 40% by weight, and evenmore preferably of from about 10% to about 20% by weight of the totalblowing agent.

In preferred embodiments in which the co-blowing agent comprises CO₂,the composition comprises CO₂ in an amount of from about 5% by weight toabout 60% by weight of the total blowing agent composition, morepreferably from about 20% by weight to about 50% by weight, and evenmore preferably of from about 40% to about 50% by weight of the totalblowing agent.

In preferred embodiments in which the co-blowing agent comprisesalcohols, (preferably C2, C3 and/or C4 alcohols), the compositioncomprises alcohol in an amount of from about 5% by weight to about 40%by weight of the total blowing agent composition, more preferably fromabout 10% by weight to about 40% by weight, and even more preferably offrom about 15% to about 25% by weight of the total blowing agent.

For compositions which include HFC co-blowing agents, the HFC co-blowingagent (preferably C2, C3, C4 and/or C5 HFC), and even more preferablydifluoromethane (HFC-152a) (HFC-152a being particularly preferred forextruded thermoplastics) and/or pentafluoropropane (HFC-245)), ispreferably present in the composition in amounts of from of from about5% by weight to about 80% by weight of the total blowing agentcomposition, more preferably from about 10% by weight to about 75% byweight, and even more preferably of from about 25% to about 75% byweight of the total blowing agent. Furthermore, in such embodiments, theHFC is preferably C2-C4 HFC, and even more preferably C3 HFC, withpenta-fluorinated C3 HFC, such as HFC-245fa, being highly preferred incertain embodiments.

For compositions which include HFE co-blowing agents, the HFE co-blowingagent (preferably C2, C3, C4 and/or C5 HFE), and even more preferablyHFE-254 (including particularly HFE-254pc) is preferably present in thecomposition in amounts of from of from about 5% by weight to about 80%by weight of the total blowing agent composition, more preferably fromabout 10% by weight to about 75% by weight, and even more preferably offrom about 25% to about 75% by weight of the total blowing agent.Furthermore, in such embodiments, the HFE is preferably C2-C4 HFE, andeven more preferably a C3 HFC, with tetra-fluorinated C3 HFE beinghighly preferred in certain embodiments.

For compositions which include HC co-blowing agents, the HC co-blowingagent (preferably C3, C4 and/or C5 HC) is preferably present in thecomposition in amounts of from of from about 5% by weight to about 80%by weight of the total blowing agent composition, and even morepreferably from about 20% by weight to about 60% by weight of the totalblowing agent.

Methods and Systems

It is contemplated that all presently known and available methods andsystems for forming foam are readily adaptable for use in connectionwith the present invention. For example, the methods of the presentinvention generally require incorporating a blowing agent in accordancewith the present invention into a foamable or foam forming compositionand then foaming the composition, preferably by a step or series ofsteps which include causing volumetric expansion of the blowing agent inaccordance with the present invention. In general, it is contemplatedthat the presently used systems and devices for incorporation of blowingagent and for foaming are readily adaptable for use in accordance withthe present invention. In fact, it is believed that one advantage of thepresent invention is the provision of an improved blowing agent which isgenerally compatible with existing foaming methods and systems.

Thus, it will be appreciated by those skilled in the art that thepresent invention comprises methods and systems for foaming all types offoams, including thermosetting foams, thermoplastic foams andformed-in-place foams. Thus, one aspect of the present invention is theuse of the present blowing agents in connection conventional foamingequipment, such as polyurethane foaming equipment, at conventionalprocessing conditions. The present methods therefore include masterbatchtype operations, blending type operations, third stream blowing agentaddition, and blowing agent addition at the foam head.

With respect to thermoplastic foams, the preferred methods generallycomprise introducing a blowing agent in accordance with the presentinvention into a thermoplastic material, preferably thermoplasticpolymer such as polyolefin, and then subjecting the thermoplasticmaterial to conditions effective to cause foaming. For example, the stepof introducing the blowing agent into the thermoplastic material maycomprise introducing the blowing agent into a screw extruder containingthe thermoplastic, and the step of causing foaming may comprise loweringthe pressure on the thermoplastic material and thereby causing expansionof the blowing agent and contributing to the foaming of the material.

It will be appreciated by those skilled in the art, especially in viewof the disclosure contained herein, that the order and manner in whichthe blowing agent of the present invention is formed and/or added to thefoamable composition does not generally affect the operability of thepresent invention. For example, in the case of extrudable foams, it ispossible that the various components of the blowing agent, and even thecomponents of the present composition, be not be mixed in advance ofintroduction to the extrusion equipment, or even that the components arenot added to the same location in the extrusion equipment. Moreover, theblowing agent can be introduced either directly or as part of a premix,which is then further added to other parts of the foamable composition.

Thus, in certain embodiments it may be desired to introduce one or morecomponents of the blowing agent at first location in the extruder, whichis upstream of the place of addition of one or more other components ofthe blowing agent, with the expectation that the components will cometogether in the extruder and/or operate more effectively in this manner.Nevertheless, in certain embodiments, two or more components of theblowing agent are combined in advance and introduced together into thefoamable composition, either directly or as part of premix which is thenfurther added to other parts of the foamable composition.

In certain preferred embodiments, dispersing agents, cell stabilizers,surfactants and other additives may also be incorporated into theblowing agent compositions of the present invention. Surfactants areoptionally but preferably added to serve as cell stabilizers. Somerepresentative materials are sold under the names of DC-193, B-8404, andL-5340 which are, generally, polysiloxane polyoxyalkylene blockco-polymers such as those disclosed in U.S. Pat. Nos. 2,834,748,2,917,480, and 2,846,458, each of which is incorporated herein byreference. Other optional additives for the blowing agent mixture mayinclude flame retardants such as tri(2-chloroethyl)phosphate,tri(2-chloropropyl)phosphate, tri(2,3-dibromopropyl)-phosphate,tri(1,3-dichloropropyl) phosphate, diammonium phosphate, varioushalogenated aromatic compounds, antimony oxide, aluminum trihydrate,polyvinyl chloride, and the like.

Any of the methods well known in the art, such as those described in“Polyurethanes Chemistry and Technology,” Volumes I and II, Saunders andFrisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporatedherein by reference, may be used or adapted for use in accordance withthe foam embodiments of the present invention.

Propellant and Aerosol Compositions

In another aspect, the present invention provides propellantcompositions comprising or consisting essentially of a composition ofthe present invention. In certain preferred embodiments, such propellantcomposition is preferably a sprayable composition, either alone or incombination with other known propellants.

In one aspect, the present compositions may be used for propellingobjects, including solid and/or liquid objects and/or gaseous objects,by applying to such objects a force generated by the presentcomposition, such as would occur through the expansion of thecompositions of the present invention. For example, such force maypreferably be provided, at least in part, by the change of phase of thecompositions of the present invention from liquid to gas, and/or by theforce released as a result of a substantial pressure reduction as thecomposition of the present invention exits from a pressurized container.In this way, the compositions of the present invention may be used toapply a burst of force, or a sustained force to an object to bepropelled. Accordingly, the present invention comprises systems,containers and devices which include compositions of the presentinvention and which are configured to propel or move an object, either aliquid object or a solid object or a gaseous object, with the desiredamount of force. Examples of such uses include containers (such aspressurized cans and similar devices) which may be used, through thepropellant force, to unblock drains, pipes or blockages in conduits,channels or nozzles. Another application includes use of the presentcomposition to propel solid objects through the environment,particularly the ambient air, such as bullets, pellets, grenades, nets,canisters, bean bags, electrodes or other individual tethered oruntethered projectiles. In other embodiments, the present compositionsmay be used to impart motion, such as a spitting motion, to gyroscopes,centrifuges, toys or other bodies to be rotated, or to impart apropelling force to solid objects, such as fireworks, confetti, pellets,munitions and other solid objects. In other applications, the forceprovided by the compositions of the present invention may be used topush or steer bodies in motion, including rockets or other projectiles.

The propellant compositions of the present invention preferably comprisea material to be sprayed and a propellant comprising, consistingessentially of, or consisting of a composition in accordance with thepresent invention. Inert ingredients, solvents, and other materials mayalso be present in the sprayable mixture. Preferably, the sprayablecomposition is an aerosol. Suitable materials to be sprayed include,without limitation, cosmetic materials such as deodorants, perfumes,hair sprays, cleaning solvents, and lubricants, as well as medicinalmaterials such as anti-asthma medications. The term medicinal materialsis used herein in its broadest sense to include any and all materialswhich are, or at least are believe to be, effective in connection withtherapeutic treatments, diagnostic methods, pain relief, and similartreatments, and as such would include for example drugs and biologicallyactive substances. The medicinal material in certain preferredembodiments are adapted to be inhaled. The medicament or othertherapeutic agent is preferably present in the composition in atherapeutic amount, with a substantial portion of the balance of thecomposition comprising a compound of Formula I of the present invention,preferably HFO-1234, and even more preferably any one or more ofcis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc,HFO-1234ye(E) and HFO-1234ye(Z).

Aerosol products for industrial, consumer or medical use typicallycontain one or more propellants along with one or more activeingredients, inert ingredients or solvents. The propellant provides theforce that expels the product in aerosolized form. While some aerosolproducts are propelled with compressed gases like carbon dioxide,nitrogen, nitrous oxide and even air, most commercial aerosols useliquefied gas propellants. The most commonly used liquefied gaspropellants are hydrocarbons such as butane, isobutane, and propane.Dimethyl ether and HFC-152a (1,1-difluoroethane) are also used, eitheralone or in blends with the hydrocarbon propellants. Unfortunately, allof these liquefied gas propellants are highly flammable and theirincorporation into aerosol formulations will often result in flammableaerosol products.

Applicants have come to appreciate the continuing need for nonflammable,liquefied gas propellants with which to formulate aerosol products. Thepresent invention provides compositions of the present invention,particularly and preferably compositions comprising HFO-1234, and evenmore preferably and one or more of cis-HFO-1234ze, trans-HFO-1234ze,HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E) and HFO-1234ye(Z), foruse in certain industrial aerosol products, including for example spraycleaners, lubricants, and the like, and in medicinal aerosols, includingfor example to deliver medications to the lungs or mucosal membranes.Examples of this includes metered dose inhalers (MDIs) for the treatmentof asthma and other chronic obstructive pulmonary diseases and fordelivery of medicaments to accessible mucous membranes or intranasally.The present invention thus includes methods for treating ailments,diseases and similar health related problems of an organism (such as ahuman or animal) comprising applying a composition of the presentinvention containing a medicament or other therapeutic component to theorganism in need of treatment. In certain preferred embodiments, thestep of applying the present composition comprises providing a MDIcontaining the composition of the present invention (for example,introducing the composition into the MDI) and then discharging thepresent composition from the MDI.

The compositions of the present invention, particularly compositionswhich comprise or consist essentially of any one or more ofcis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc,HFO-1234ye(E) and HFO-1234ye(Z), are capable of providing nonflammable,liquefied gas propellant and aerosols that do not contributesubstantially to global warming. The present compositions can be used toformulate a variety of industrial aerosols or other sprayablecompositions such as contact cleaners, dusters, lubricant sprays, andthe like, and consumer aerosols such as personal care products,household products and automotive products. HFO-1234ze is particularlypreferred for use as an important component of propellant compositionsfor in medicinal aerosols such as metered dose inhalers. The medicinalaerosol and/or propellant and/or sprayable compositions of the presentinvention in many applications include, in addition to compound offormula (I) or (II) (preferably any one or more of cis-HFO-1234ze,trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E) andHFO-1234ye(Z)), a medicament such as a beta-agonist, a corticosteroid orother medicament, and, optionally, other ingredients, such assurfactants, solvents, other propellants, flavorants and otherexcipients. The compositions of the present invention, unlike manycompositions previously used in these applications, have goodenvironmental properties and are not considered to be potentialcontributors to global warming. The present compositions thereforeprovide in certain preferred embodiments substantially nonflammable,liquefied gas propellants having very low Global Warming potentials.

Flavorants and Fragrances

The compositions of the present invention also provide advantage whenused as part of, and in particular as a carrier for, flavor formulationsand fragrance formulations. The suitability of the present compositionsfor this purpose is demonstrated by a test procedure in which 0.39 gramsof Jasmone were put into a heavy walled glass tube. 1.73 grams ofR-1234ze were added to the glass tube. The tube was then frozen andsealed. Upon thawing the tube, it was found that the mixture had oneliquid phase. The solution contained 20 wt. % Jasome and 80 wt. %R-1234ze, thus establishing favorable use a carrier for flavorformulations and fragrances. It also establishes its potential as anextractant of biologically active compounds (such as Biomass) andfragrances, including from plant matter. In certain embodiments, it maybe preferred to use the present composition for in extractionapplications with the present fluid in its supercritical state. This another applications of involving use of the present compositions in thesupercritical or near supercritical state are described hereinafter.

Inflating Agents

One potential advantage of the compositions of the present invention isthat the preferred compositions are in a gaseous state under mostambient conditions. This characteristic allows them to fill the spacewhile not adding significantly to the weight of the space being spilled.Furthermore, the compositions of the present invention are able to becompressed or liquefied for relatively easy transportation and storage.Thus, for example, the compositions of the present invention may beincluded, preferably but not necessarily in liquid form, in a closedcontainer, such as a pressurized can, which has a nozzle therein adaptedto release the composition into another environment in which it willexist, at least for a period of time, as a pressurized gas. For example,such an application may include including the present compositions in acan adapted to connect to tires such as may be used on transportationvehicles (including cars, trucks and aircraft). Other examples inaccordance with this embodiment include the use of the presentcompositions, in a similar arrangement, to inflate air bags or otherbladders (including other protective bladders) adapted to contain, atleast for a period of time, a gaseous material under pressure.Alternatively to the use of a fixed container, such as I can, thepresent compositions may be applied in accordance with this aspect ofthe invention through a hose or other system that contains the presentcomposition, either in liquid or gaseous form, and through which it canbe introduced into such a pressurized environment as is required for theparticular application.

Methods and Systems

The compositions of the present invention are useful in connection withnumerous methods and systems, including as heat transfer fluids inmethods and systems for transferring heat, such as refrigerants used inrefrigeration, air conditioning and heat pump systems. The presentcompositions are also advantageous for in use in systems and methods ofgenerating aerosols, preferably comprising or consisting of the aerosolpropellant in such systems and methods. Methods of forming foams andmethods of extinguishing and suppressing fire are also included incertain aspects of the present invention. The present invention alsoprovides in certain aspects methods of removing residue from articles inwhich the present compositions are used as solvent compositions in suchmethods and systems.

Heat Transfer Methods and Systems

The preferred heat transfer methods generally comprise providing acomposition of the present invention and causing heat to be transferredto or from the composition, either by sensible heat transfer, phasechange heat transfer, or a combination of these. For example, in certainpreferred embodiments the present methods provide refrigeration systemscomprising a refrigerant of the present invention and methods ofproducing heating or cooling by condensing and/or evaporating acomposition of the present invention. In certain preferred embodiments,the methods for cooling, including cooling of other fluid eitherdirectly or indirectly or a body directly or indirectly, comprisecondensing a refrigerant composition comprising a composition of thepresent invention and thereafter evaporating said refrigerantcomposition in the vicinity of the article to be cooled. As used herein,the term “body” is intended to refer not only to inanimate objects butalso to living tissue, including animal tissue in general and humantissue in particular. For example, certain aspects of the presentinvention involve application of the present composition to human tissuefor one or more therapeutic purposes, such as a pain killing technique,as a preparatory anesthetic, or as part of a therapy involving reducingthe temperature of the body being treated. In certain embodiments, theapplication to the body comprises providing the present compositions inliquid form under pressure, preferably in a pressurized container havinga one-way discharge valve and/or nozzle, and releasing the liquid fromthe pressurized container by spraying or otherwise applying thecomposition to the body. As the liquid evaporates from the surface beingsprayed, the surface cools.

Certain preferred methods for heating a fluid or body comprisecondensing a refrigerant composition comprising a composition of thepresent invention in the vicinity of the fluid or body to be heated andthereafter evaporating said refrigerant composition. In light of thedisclosure herein, those of skill in the art will be readily able toheat and cool articles according to the present inventions without undueexperimentation.

Applicants have found that in the systems and methods of the presentinvention many of the important refrigeration system performanceparameters are relatively close to the parameters for R-134a. Since manyexisting refrigeration systems have been designed for R-134a, or forother refrigerants with properties similar to R-134a, those skilled inthe art will appreciate the substantial advantage of a low GWP and/or alow ozone depleting refrigerant that can be used as replacement forR-134a or like refrigerants with relatively minimal modifications to thesystem. It is contemplated that in certain embodiments the presentinvention provides retrofitting methods which comprise replacing theheat transfer fluid (such as a refrigerant) in an existing system with acomposition of the present invention, without substantial modificationof the system. In certain preferred embodiments the replacement step isa drop-in replacement in the sense that no substantial redesign of thesystem is required and no major item of equipment needs to be replacedin order to accommodate the composition of the present invention as theheat transfer fluid. In certain preferred embodiments, the methodscomprise a drop-in replacement in which the capacity of the system is atleast about 70%, preferably at least about 85%, and even more preferablyat least about 90% of the system capacity prior to replacement. Incertain preferred embodiments, the methods comprise a drop-inreplacement in which the suction pressure and/or the discharge pressureof the system, and even more preferably both, is/are at least about 70%,more preferably at least about 90% and even more preferably at leastabout 95% of the suction pressure and/or the discharge pressure prior toreplacement. In certain preferred embodiments, the methods comprise adrop-in replacement in which the mass flow of the system is at leastabout 80%, and even more preferably at least 90% of the mass flow priorto replacement.

In certain embodiments the present invention provides cooling byabsorbing heat from a fluid or body, preferably by evaporating thepresent refrigerant composition in the vicinity of the body or fluid tobe cooled to produce vapor comprising the present composition.Preferably the methods include the further step of compressing therefrigerant vapor, usually with a compressor or similar equipment toproduce vapor of the present composition at a relatively elevatedpressure. Generally, the step of compressing the vapor results in theaddition of heat to the vapor, thus causing an increase in thetemperature of the relatively high pressure vapor. Preferably in suchembodiments the present methods include removing from this relativelyhigh temperature, high pressure vapor at least a portion of the heatadded by the evaporation and compression steps. The heat removal steppreferably includes condensing the high temperature, high pressure vaporwhile the vapor is in a relatively high pressure condition to produce arelatively high pressure liquid comprising a composition of the presentinvention. This relatively high pressure liquid preferably thenundergoes a nominally isoenthalpic reduction in pressure to produce arelatively low temperature, low pressure liquid. In such embodiments, itis this reduced temperature refrigerant liquid which is then vaporizedby heat transferred from the body or fluid to be cooled.

In another process embodiment of the invention, the compositions of theinvention may be used in a method for producing heating which comprisescondensing a refrigerant comprising the compositions in the vicinity ofa liquid or body to be heated. Such methods, as mentioned hereinbefore,frequently are reverse cycles to the refrigeration cycle describedabove.

Foam Blowing Methods

One embodiment of the present invention relates to methods of formingfoams, and preferably polyurethane and polyisocyanurate foams. Themethods generally comprise providing a blowing agent composition of thepresent inventions, adding (directly or indirectly) the blowing agentcomposition to a foamable composition, and reacting the foamablecomposition under the conditions effective to form a foam or cellularstructure, as is well known in the art. Any of the methods well known inthe art, such as those described in “Polyurethanes Chemistry andTechnology,” Volumes I and II, Saunders and Frisch, 1962, John Wiley andSons, New York, N.Y., which is incorporated herein by reference, may beused or adapted for use in accordance with the foam embodiments of thepresent invention. In general, such preferred methods comprise preparingpolyurethane or polyisocyanurate foams by combining an isocyanate, apolyol or mixture of polyols, a blowing agent or mixture of blowingagents comprising one or more of the present compositions, and othermaterials such as catalysts, surfactants, and optionally, flameretardants, colorants, or other additives.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in pre-blended formulations. Mosttypically, the foam formulation is pre-blended into two components. Theisocyanate and optionally certain surfactants and blowing agentscomprise the first component, commonly referred to as the “A” component.The polyol or polyol mixture, surfactant, catalysts, blowing agents,flame retardant, and other isocyanate reactive components comprise thesecond component, commonly referred to as the “B” component.Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A and B side components either by hand mix forsmall preparations and, preferably, machine mix techniques to formblocks, slabs, laminates, pour-in-place panels and other items, sprayapplied foams, froths, and the like. Optionally, other ingredients suchas fire retardants, colorants, auxiliary blowing agents, and even otherpolyols can be added as a third stream to the mix head or reaction site.Most preferably, however, they are all incorporated into one B-componentas described above.

It is also possible to produce thermoplastic foams using thecompositions of the invention. For example, conventional polystyrene andpolyethylene formulations may be combined with the compositions in aconventional manner to produce rigid foams.

Cleaning Methods

The present invention also provides methods of removing containmentsfrom a product, part, component, substrate, or any other article orportion thereof by applying to the article a composition of the presentinvention. For the purposes of convenience, the term “article” is usedherein to refer to all such products, parts, components, substrates, andthe like and is further intended to refer to any surface or portionthereof. Furthermore, the term “contaminant” is intended to refer to anyunwanted material or substance present on the article, even if suchsubstance is placed on the article intentionally. For example, in themanufacture of semiconductor devices it is common to deposit aphotoresist material onto a substrate to form a mask for the etchingoperation and to subsequently remove the photoresist material from thesubstrate. The term “contaminant” as used herein is intended to coverand encompass such a photo resist material.

Preferred methods of the present invention comprise applying the presentcomposition to the article. Although it is contemplated that numerousand varied cleaning techniques can employ the compositions of thepresent invention to good advantage, it is considered to be particularlyadvantageous to use the present compositions in connection withsupercritical cleaning techniques. Supercritical cleaning is disclosedin U.S. Pat. No. 6,589,355, which is assigned to the assignee of thepresent invention and incorporated herein by reference. Forsupercritical cleaning applications, is preferred in certain embodimentsto include in the present cleaning compositions, in addition to theHFO-1234 (preferably any one or more of cis-HFO-1234ze,trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E) andHFO-1234ye(Z)), one or more additional components, such as CO₂ and otheradditional components known for use in connection with supercriticalcleaning applications. It may also be possible and desirable in certainembodiments to use the present cleaning compositions in connection withparticular vapor degreasing and solvent cleaning methods.

Flammability Reduction Methods

According to certain other preferred embodiments, the present inventionprovides methods for reducing the flammability of fluids, said methodscomprising adding a compound or composition of the present invention tosaid fluid. The flammability associated with any of a wide range ofotherwise flammable fluids may be reduced according to the presentinvention. For example, the flammability associated with fluids such asethylene oxide, flammable hydrofluorocarbons and hydrocarbons,including: HFC-152a, 1,1,1-trifluoroethane (HFC-143a), difluoromethane(HFC-32), propane, hexane, octane, and the like can be reduced accordingto the present invention. For the purposes of the present invention, aflammable fluid may be any fluid exhibiting flammability ranges in airas measured via any standard conventional test method, such as ASTME-681, and the like.

Any suitable amounts of the present compounds or compositions may beadded to reduce flammability of a fluid according to the presentinvention. As will be recognized by those of skill in the art, theamount added will depend, at least in part, on the degree to which thesubject fluid is flammable and the degree to which it is desired toreduce the flammability thereof. In certain preferred embodiments, theamount of compound or composition added to the flammable fluid iseffective to render the resulting fluid substantially non-flammable.

Flame Suppression Methods

The present invention further provides methods of suppressing a flame,said methods comprising contacting a flame with a fluid comprising acompound or composition of the present invention. Any suitable methodsfor contacting the flame with the present composition may be used. Forexample, a composition of the present invention may be sprayed, poured,and the like onto the flame, or at least a portion of the flame may beimmersed in the composition. In light of the teachings herein, those ofskill in the art will be readily able to adapt a variety of conventionalapparatus and methods of flame suppression for use in the presentinvention.

Sterilization Methods

Many articles, devices and materials, particularly for use in themedical field, must be sterilized prior to use for the health and safetyreasons, such as the health and safety of patients and hospital staff.The present invention provides methods of sterilizing comprisingcontacting the articles, devices or material to be sterilized with acompound or composition of the present invention comprising a compoundof Formula I, preferably HFO-1234, and even more preferably any one ormore of cis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc,HFO-1234zc, HFO-1234ye(E) and HFO-1234ye(Z), in combination with one ormore sterilizing agents. While many sterilizing agents are known in theart and are considered to be adaptable for use in connection with thepresent invention, in certain preferred embodiments sterilizing agentcomprises ethylene oxide, formaldehyde, hydrogen peroxide, chlorinedioxide, ozone and combinations of these. In certain embodiments,ethylene oxide is the preferred sterilizing agent. Those skilled in theart, in view of the teachings contained herein, will be able to readilydetermine the relative proportions of sterilizing agent and the presentcompound(s) to be used in connection with the present sterilizingcompositions and methods, and all such ranges are within the broad scopehereof. As is known to those skilled in the art, certain sterilizingagents, such as ethylene oxide, are relatively flammable components, andthe compound(s) in accordance with the present invention are included inthe present compositions in amounts effective, together with othercomponents present in the composition, to reduce the flammability of thesterilizing composition to acceptable levels.

The sterilization methods of the present invention may be either high orlow-temperature sterilization of the present invention involves the useof a compound or composition of the present invention at a temperatureof from about 250° F. to about 270° F., preferably in a substantiallysealed chamber. The process can be completed usually in less than about2 hours. However, some articles, such as plastic articles and electricalcomponents, cannot withstand such high temperatures and requirelow-temperature sterilization. In low temperature sterilization methods,the article to be sterilized is exposed to a fluid comprising acomposition of the present invention at a temperature of from about roomtemperature to about 200° F., more preferably at a temperature of fromabout room temperature to about 100° F.

The low-temperature sterilization of the present invention is preferablyat least a two-step process performed in a substantially sealed,preferably air tight, chamber. In the first step (the sterilizationstep), the articles having been cleaned and wrapped in gas permeablebags are placed in the chamber. Air is then evacuated from the chamberby pulling a vacuum and perhaps by displacing the air with steam. Incertain embodiments, it is preferable to inject steam into the chamberto achieve a relative humidity that ranges preferably from about 30% toabout 70%. Such humidities may maximize the sterilizing effectiveness ofthe sterilant which is introduced into the chamber after the desiredrelative humidity is achieved. After a period of time sufficient for thesterilant to permeate the wrapping and reach the interstices of thearticle, the sterilant and steam are evacuated from the chamber.

In the preferred second step of the process (the aeration step), thearticles are aerated to remove sterilant residues. Removing suchresidues is particularly important in the case of toxic sterilants,although it is optional in those cases in which the substantiallynon-toxic compounds of the present invention are used. Typical aerationprocesses include air washes, continuous aeration, and a combination ofthe two. An air wash is a batch process and usually comprises evacuatingthe chamber for a relatively short period, for example, 12 minutes, andthen introducing air at atmospheric pressure or higher into the chamber.This cycle is repeated any number of times until the desired removal ofsterilant is achieved. Continuous aeration typically involvesintroducing air through an inlet at one side of the chamber and thendrawing it out through an outlet on the other side of the chamber byapplying a slight vacuum to the outlet. Frequently, the two approachesare combined. For example, a common approach involves performing airwashes and then an aeration cycle.

Supercritical Methods

It is contemplated that in general many of the uses and methodsdescribed herein can be carried out with the present compositions in thesupercritical or near supercritical state. For example, the presentcompositions may be utilized in solvent and solvent extractionapplications mentioned herein, particularly for use in connection withmaterials such as alkaloids (which are commonly derived from plantsources), for example caffeine, codeine and papaverine, fororganometallic materials such as metallocenes, which are generallyuseful as catalysts, and for fragrances and flavors such as Jasmone.

The present compositions, preferably in their supercritical or nearsupercritical state, can be used in connection with methods involvingthe deposit of catalysts, particularly organometallic catalysts, onsolid supports. In one preferred embodiment, these methods include thestep of generating finely divided catalyst particles, preferably byprecipitating such catalyst particles from the present compositions inthe supercritical or near supercritical state. It is expected that incertain preferred embodiments catalysts prepared in accordance with thepresent methods will exhibit excellent activity.

It is also contemplated that certain of the MDI methods and devicesdescribed herein may utilize medicaments in finely divided form, and insuch situations it is contemplated that the present invention providesmethods which include the step of incorporating such finely dividedmedicament particles, such as albuterol, into the present fluids,preferably by dissolving such particles, in the present composition,preferably in the supercritical or near supercritical state. In caseswhere the solubility of the materials is relatively low when the presentfluids are in the supercritical or near supercritical state, it may bepreferred to use entrainers such as alcohols.

It is also contemplated that the present compositions in thesupercritical or near supercritical state may be used to clean circuitboards and other electronic materials and articles.

Certain materials may have very limited solubility in the presentcompositions, particularly when in the supercritical or nearsupercritical state. For such situations, the present compositions maybe used as anti-solvents for the precipitation of such low solubilitysolutes from solution in another supercritical or near supercriticalsolvent, such as carbon dioxide. For example, supercritical carbondioxide is utilized frequently used in the extrusion process ofthermoplastic foams, and the present compositions may be used toprecipitation certain materials contained therein.

It is contemplated also that in certain embodiments it may be desirableto utilize the present compositions when in the supercritical or nearsupercritical state as a blowing agent.

The present methods and systems also include forming a one componentfoam, preferably polyurethane foam, containing a blowing agent inaccordance with the present invention. In certain preferablyembodiments, a portion of the the blowing agent is contained in the foamforming agent, preferably by being dissolved in a foam forming agentwhich is liquid at the pressure within the container, a second portionof the blowing agent is present as a separate gas phase. In suchsystems, the contained/dissolved blowing agent performs, in large part,to cause the expansion of the foam, and the separate gas phase operatesto impart propulsive force to the foam forming agent. Such one componentsystems are typically and preferably packaged in a container, such as anaerosol type can, and the blowing agent of the present invention thuspreferably provides for expansion of the foam and/or the energy totransport the foam/foamable material from the package, and preferablyboth. In certain embodiments, such systems and methods comprise chargingthe package with a fully formulated system (preferably isocyanate/polyolsystem) and incorporating a gaseous blowing agent in accordance with thepresent invention into the package, preferably an aerosol type can.

Any of the methods well known in the art, such as those described in“Polyurethanes Chemistry and Technology,” Volumes I and II, Saunders andFrisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporatedherein by reference, may be used or adapted for use in accordance withthe foam forming embodiments of the present invention.

It is contemplated also that in certain embodiments it may be desirableto utilize the present compositions when in the supercritical or nearsupercritical state as a blowing agent.

The Foams

The invention also relates to all foams, (incuding but not limited toclosed cell foam, open cell foam, rigid foam, flexible foam, integeralskin and the like) prepared from a polymer foam formulation containing ablowing agent comprising the compositions of the invention. Applicantshave found that one advantage of the foams, and particularly thermosetfoams such as polyurethane foams, in accordance with the presentinvention is the ability to achieve, preferably in connection withthermoset foam embodiments, exceptional thermal performance, such as canbe measured by the K-factor or lambda, particularly and preferably underlow temperature conditions. Although it is contemplated that the presentfoams, particularly thermoset foams of the present invention, may beused in a wide variety of applications, in certain preferred embodimentsthe present invention comprises appliance foams in accordance with thepresent invention, including refrigerator foams, freezer foams,refrigerator/freezer foams, panel foams, and other cold or cryogenicmanufacturing applications.

The foams in accordance with the present invention, in certain preferredembodiments, provide one or more exceptional features, characteristicsand/or properties, including: thermal insulation efficiency(particularly for thermoset foams), dimensional stability, compressivestrength, aging of thermal insulation properties, all in addition to thelow ozone depletion potential and low global warming potentialassociated with many of the preferred blowing agents of the presentinvention. In certain highly preferred embodiments, the presentinvention provides thermoset foam, including such foam formed into foamarticles, which exhibit improved thermal conductivity relative to foamsmade using the same blowing agent (or a commonly used blowing agentHFC-245fa) in the same amount but without the compound of Formula I inaccordance with the present invention. In certain highly preferredembodiments, the thermoset foams, and preferably polyurethane foams, ofthe present invention exhibit a K-factor (BTU in/hr ft² ° F.) at 40° F.of not greater than about 0.14, more preferably not greater than 0.135,and even more preferably not greater than 0.13. Furthermore, in certainembodiments, it is preferred that the thermoset foams, and preferablythe polyurethane foams of the present invention exhibit a K-factor (BTUin/hr ft² ° F.) at 75° F. of not greater than about 0.16, morepreferably not greater than 0.15, and even more preferably not greaterthan 0.145.

In other preferred embodiments, the present foams exhibit improvedmechanical properties relative to foams produced with blowing agentsoutside the scope of the present invention. For example, certainpreferred embodiments of the present invention provide foams and foamarticles having a compressive strength which is superior to, andpreferably at least about 10 relative percent, and even more preferablyat least about 15 relative percent greater than a foam produced undersubstantially identical conditions by utilizing a blowing agentconsisting of cyclopentane. Furthermore, it is preferred in certainembodiments that the foams produced in accordance with the presentinvention have compressive strengths that are on a commercial basiscomparable to the compressive strength produced by making a foam undersubstantially the same conditions except wherein the blowing agentconsists of HFC-245fa. In certain preferred embodiments, the foams ofthe present invention exhibit a compressive strength of at least about12.5% yield (in the parallel and perpendicular directions), and evenmore preferably at least about 13% yield in each of said directions.

EXAMPLES

The following examples are provided for the purpose of illustrating thepresent invention but without limiting the scope thereof.

Example 1

The coefficient of performance (COP) is a universally accepted measureof refrigerant performance, especially useful in representing therelative thermodynamic efficiency of a refrigerant in a specific heatingor cooling cycle involving evaporation or condensation of therefrigerant. In refrigeration engineering, this term expresses the ratioof useful refrigeration to the energy applied by the compressor incompressing the vapor. The capacity of a refrigerant represents theamount of cooling or heating it provides and provides some measure ofthe capability of a compressor to pump quantities of heat for a givenvolumetric flow rate of refrigerant. In other words, given a specificcompressor, a refrigerant with a higher capacity will deliver morecooling or heating power. One means for estimating COP of a refrigerantat specific operating conditions is from the thermodynamic properties ofthe refrigerant using standard refrigeration cycle analysis techniques(see for example, R. C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK,Chapter 3, Prentice-Hall, 1988).

A refrigeration/air conditioning cycle system is provided where thecondenser temperature is about 150° F. and the evaporator temperature isabout −35° F. under nominally isentropic compression with a compressorinlet temperature of about 50° F. COP is determined for severalcompositions of the present invention over a range of condenser andevaporator temperatures and reported in Table 1 below, based uponHFC-134a having a COP value of 1.00, a capacity value of 1.00 and adischarge temperature of 175° F.

TABLE 1 DISCHARGE REFRIGERANT Relative TEMPERATURE COMPOSTION RelativeCOP CAPACITY (° F.) HFO 1225ye 1.02 0.76 158 HFO trans-1234ze 1.04 0.70165 HFO cis-1234ze 1.13 0.36 155 HFO 1234yf 0.98 1.10 168

This example shows that certain of the preferred compounds for use withthe present compositions each have a better energy efficiency thanHFC-134a (1.02, 1.04 and 1.13 compared to 1.00) and the compressor usingthe present refrigerant compositions will produce discharge temperatures(158, 165 and 155 compared to 175), which is advantageous since suchresult will likely leading to reduced maintenance problems. Moreover, itis evident from the above table that one embodiment of the presentinvention, namely one in which the refrigerant composition comprises,and preferably comprises at least about 70% by weight of HFO-1234yf, hasa dramatically superior performance in terms of relative capacity incomparison not only to R-134a, but also to embodiments in which therefrigerant consists essentially of HFO-1234ze. In certain preferredembodiments, therefore the present invention provides methods forheating or cooling an article or fluid comprising using a compositioncomprising at least about 80% by weight of HFO-1234yf, and even morepreferably at least about 90% by weight, and in which the capacity ofthe refrigeration system is at least about 100%, more preferably atleast about 105%, of the capacity of the same system with R-134a used asthe refrigerant.

Example 2

The miscibility of HFO-1225ye and HFO-1234ze with various refrigerationlubricants is tested. The lubricants tested are mineral oil (C3), alkylbenzene (Zerol 150), ester oil (Mobil EAL 22 cc and Solest 120),polyalkylene glycol (PAG) oil (Goodwrench Refrigeration Oil for 134asystems), and a poly(alpha-olefin) oil (CP-6005-100). For eachrefrigerant/oil combination, three compositions are tested, namely 5, 20and 50 weight percent of lubricant, with the balance of each being thecompound of the present invention being tested

The lubricant compositions are placed in heavy-walled glass tubes. Thetubes are evacuated, the refrigerant compound in accordance with thepresent invention is added, and the tubes are then sealed. The tubes arethen put into an air bath environmental chamber, the temperature ofwhich is varied from about −50° C. to 70° C. At roughly 10° C.intervals, visual observations of the tube contents are made for theexistence of one or more liquid phases. In a case where more than oneliquid phase is observed, the mixture is reported to be immiscible. In acase where there is only one liquid phase observed, the mixture isreported to be miscible. In those cases where two liquid phases wereobserved, but with one of the liquid phases occupying only a very smallvolume, the mixture is reported to be partially miscible.

The polyalkylene glycol and ester oil lubricants were judged to bemiscible in all tested proportions over the entire temperature range,except that for the HFO-1225ye mixtures with polyalkylene glycol, therefrigerant mixture was found to be immiscible over the temperaturerange of −50° C. to −30° C. and to be partially miscible over from −20to 50° C. At 50 weight percent concentration of the PAG in refrigerantand at 60°, the refrigerant/PAG mixture was miscible. At 70° C., it wasmiscible from 5 weight percent lubricant in refrigerant to 50 weightpercent lubricants in refrigerant.

Example 3

The compatibility of the refrigerant compounds and compositions of thepresent invention with PAG lubricating oils while in contact with metalsused in refrigeration and air conditioning systems is tested at 350° C.,representing conditions much more severe than are found in manyrefrigeration and air conditioning applications.

Aluminum, copper and steel coupons are added to heavy walled glasstubes. Two grams of oil are added to the tubes. The tubes are thenevacuated and one gram of refrigerant is added. The tubes are put intoan oven at 350° F. for one week and visual observations are made. At theend of the exposure period, the tubes are removed.

This procedure was done for the following combinations of oil and thecompound of the present invention:

-   -   a) HFC-1234ze and GM Goodwrench PAG oil    -   b) HFC1243 zf and GM Goodwrench oil PAG oil    -   c) HFC-1234ze and MOPAR-56 PAG oil    -   d) HFC-1243 zf and MOPAR-56 PAG oil    -   e) HFC-1225 ye and MOPAR-56 PAG oil.

In all cases, there is minimal change in the appearance of the contentsof the tube. This indicates that the refrigerant compounds andcompositions of the present invention are stable in contact withaluminum, steel and copper found in refrigeration and air conditioningsystems, and the types of lubricating oils that are likely to beincluded in such compositions or used with such compositions in thesetypes of systems.

Comparative Example

Aluminum, copper and steel coupons are added to a heavy walled glasstube with mineral oil and CFC-12 and heated for one week at 350° C., asin Example 3. At the end of the exposure period, the tube is removed andvisual observations are made. The liquid contents are observed to turnblack, indicating there is severe decomposition of the contents of thetube.

CFC-12 and mineral oil have heretofore been the combination of choice inmany refrigerant systems and methods. Thus, the refrigerant compoundsand compositions of the present invention possess significantly betterstability with many commonly used lubricating oils than the widely-usedprior art refrigerant-lubricating oil combination.

Example 4 Polyol Foam

This example illustrates the use of blowing agent in accordance with oneof the preferred embodiments of the present invention, namely the use ofHFO-1234ze, and the production of polyol foams in accordance with thepresent invention. The components of a polyol foam formulation areprepared in accordance with the following Table 2:

TABLE 2 PBW Polyol Component Voranol 490 50 Voranol 391 50 Water 0.5B-8462 (surfactant) 2.0 Polycat 8 0.3 Polycat 41 3.0 HFO-1234ze 35 Total140.8 Isocyanate M-20S 123.8 Index 1.10 *Voranol 490 is a sucrose-basedpolyol and Voranol 391 is a toluene diamine based polyol, and each arefrom Dow Chemical. B-8462 is a surfactant available fromDegussa-Goldschmidt. Polycat catalysts are tertiary amine based and areavailable from Air Products. Isocyanate M-20S is a product of Bayer LLC.

Degussa-Goldschmidt. Polycat catalysts are tertiary amine based and areavailable from Air Products. Isocyanate M-20S is a product of Bayer LLC.

The foam is prepared by first mixing the ingredients thereof, butwithout the addition of blowing agent. Two Fisher-Porter tubes are eachfilled with about 52.6 grams of the polyol mixture (without blowingagent) and sealed and placed in a refrigerator to cool and form a slightvacuum. Using gas burets, about 17.4 grams of HFO-1234ze are added toeach tube, and the tubes are then placed in an ultrasound bath in warmwater and allowed to sit for 30 minutes. The solution produced is hazy,and a vapor pressure measurement at room temperature indicates a vaporpressure of about 70 psig indicating that the blowing agent is not insolution. The tubes are then placed in a freezer at 27° F. for 2 hours.The vapor pressure was again measured and found to be 14-psig. Theisocyanate mixture, about 87.9 grams, is placed into a metal containerand placed in a refrigerator and allowed to cool to about 50° F. Thepolyol tubes were then opened and weighed into a metal mixing container(about 100 grams of polyol blend are used). The isocyanate from thecooled metal container is then immediately poured into the polyol andmixed with an air mixer with double propellers at 3000 RPM's for 10seconds. The blend immediately begins to froth with the agitation and isthen poured into an 8×8×4 inch box and allowed to foam. Because of thefroth, a cream time can not be measured. The foam has a 4-minute geltime and a 5-minute tack free time. The foam is then allowed to cure fortwo days at room temperature.The foam is then cut to samples suitable for measuring physicalproperties and is found to have a density of 2.14 pcf. K-factors aremeasured and found to be as indicated in the following Table 3:

TABLE 3 Temperature K, BTU In/Ft² h ° F. 40° F. 0.1464 75° F. 0.1640110° F.  0.1808

Example 5 Polstyrene Foam

This example illustrates the use of blowing agent in accordance with twopreferred embodiments of the present invention, namely the use ofHFO-1234ze and HFO-1234yf, and the production of polystyrene foam. Atesting apparatus and protocol has been established as an aid todetermining whether a specific blowing agent and polymer are capable ofproducing a foam and the quality of the foam. Ground polymer (DowPolystyrene 685D) and blowing agent consisting essentially of HFO-1234zeare combined in a vessel. The vessel volume is 200 cm³ and it is madefrom two pipe flanges and a section of 2-inch diameter schedule 40stainless steel pipe 4 inches long. The vessel is placed in an oven,with temperature set at from about 190° F. to about 285° F., preferablyfor polystyrene at 265° F., and remains there until temperatureequilibrium is reached.

The pressure in the vessel is then released, quickly producing a foamedpolymer. The blowing agent plasticizes the polymer as it dissolves intoit. The resulting density of the two foams thus produced using thismethod are given in Table 4. The data show that foam polystyrene isobtainable in accordance with the present invention. The die temperaturefor R1234ze with polystyrene is about 250° F.

TABLE 4 Dow polystyrene 685D Foam density (lb/ft³) T ° F.transHFO-1234ze HFO-1234yf 275 55.15 260 22.14 14.27 250 7.28 24.17 24016.93This example demonstrates the performance of HFO-1234ze alone as ablowing agent for polystyrene foam formed in a twin screw type extruder.The apparatus employed in this example is a Leistritz twin screwextruder having the following characteristics:

-   30 mm co-rotating screws-   L:D Ratio=40:1-   The extruder is divided into 10 sections, each representing a L:D of    4:1.    The polystyrene resin was introduced into the first section, the    blowing agent was introduced into the sixth section, with the    extrudate exiting the tenth section. The extruder operated primarily    as a melt/mixing extruder. A subsequent cooling extruder is    connected in tandem, for which the design characteristics were:-   Leistritz twin screw extruder-   40 mm co-rotating screws-   L:D Ratio=40:1-   Die: 5.0 mm circular    Polystyrene resin, namely Nova Chemical—general extrusion grade    polystyrene, identified as Nova 1600, is feed to the extruder under    the conditions indicated above. The resin has a recommended melt    temperature of 375° F. 525° F. The pressure of the extruder at the    die is about 1320 pounds per square inch (psi), and the temperature    at the die is about 115 ° C.    A blowing agent consisting essentially of transHFO-1234ze is added    to the extruder at the location indicated above, with about 0.5% by    weight of talc being included, on the basis of the total blowing    agent, as a nucleating agent. Foam is produced using the blowing    agent at concentrations of 10% by weight, 12% by weight, and 14% by    weight, in accordance with the present invention. The density of the    foam produced is in the range of about 0.1 grams per cubic    centimeter to 0.07 grams per cubic centimeter, with a cell size of    about 49 to about 68 microns. The foams, of approximately 30    millimeters diameter, are visually of very good quality, very fine    cell size, with no visible or apparent blow holes or voids.

Example 5A Polystyrene Foam

This procedure of Example 5 is repeated except that the foaming agentcomprises about 50% by weight transHFO-1234ze and 50% by weight ofHFC-245fa and nucleating agent in the concentration indicated in Example5. Foamed polystyrene is prepared at blowing agent concentrations ofapproximately 10% and 12%. The density of the foam produced is about0.09 grams per cubic centimeter, with a cell size of about 200 microns.The foams, of approximately 30 millimeters diameter, are visually ofvery good quality, fine cell structure, with no visible or apparentvoids.

Example 5B Polystyrene Foam

This procedure of Example 5 is repeated except that the foaming agentcomprises about 80% by weight transHFO-1234ze and 20% by weight ofHFC-245fa and nucleating agent in the concentration indicated in Example5. Foamed polystyrene is prepared at blowing agent concentrations ofapproximately 10% and 12%. The density of the foam produced is about0.08 grams per cubic centimeter, with a cell size of about 120 microns.The foams, of approximately 30 millimeters diameter, are visually ofvery good quality, fine cell structure, with no visible or apparentvoids.

Example 5C Polystyrene Foam

This procedure of Example 5 is repeated with trans HFO-1234ze exceptthat the nucleating agent is omitted. The foams' density was in therange of 0.1 grams per cubic centimeter, and the cell size diameter isabout 400. The foams, of approximately 30 millimeters diameter, arevisually of very good quality, fine cell structure, with no visible orapparent voids.

Example 6 Polyurethane Foam Compressive Strength

This example demonstrates the performance of HFO-1234ze, and isomersthereof, used in combination with hydrocarbon co-blowing agents, and inparticular the utility of compositions comprising HFO-1234ze andcyclopentane co-blowing agents in compressive strength performance ofpolyurethane foams.

A commercially available, refrigeration appliance-type polyurethane foamformulation (foam forming agent) is provided. The polyol blend consistedof commercial polyol(s), catalyst(s), and surfactant(s). Thisformulation is adapted for use in connection with a gaseous blowingagent. Standard commercial polyurethane processing equipment is used forthe foam forming process. A gaseous blowing agent combination was formedcomprising HFO-1234ze (including isomers thereof) in a concentration ofapproximately 60 mole percent, and cyclopentane in a concentration ofapproximately 40 mole percent of the total blowing agent. This exampleillustrates the physical property performance of combinations ofHFO-1234ze (including isomers thereof) in combination with cyclopentaneco-blowing agent. Table 5 below reports the compressive strength ofsimilar machine-made polyurethane foams using a blowing agent of thepresent invention in comparison to foams made using a blowing agentconsisting of HFC-245fa and a blowing agent consisting of cyclopentane.

TABLE 5 Compressive Strength Parallel Perpendicular Blowing Agent %Yield % Yield HFO1234ze/cyclopentane 13.513 14.672 HFC-245fa 13.88114.994 Cyclopentane 11.462 10.559

One unexpected result illustrated by this example is the ability toprocess HFO-1234ze, and HFC-1234ze/HFC blends in conventional foamprocessing equipment, and polyurethane processing equipment inparticular. This is potentially of a great advantage in so far that itpermits foam processing with various types of systems and equipment,including: masterbatch type blending equipment, gaseous blowing agentblending equipment, third stream addition of the blowing agent, orblowing agent addition at the foam head.

Example 7 Polyurethane Foam K-Factors

A polyurethane foam is prepared and is adapted for use as a commercial“appliance type” polyurethane formulation. The same foam formulationdescribed in Example 6 is used in connection with the same standardcommercial polyurethane processing equipment is used in the foam formingprocess. Several systems are prepared, with each system using identicalcomponents, systems, and equipment, with the exception of the blowingagent. In addition to blowing agent in accordance with the presentinvention, HFC-134a, HFC-245fa, and cyclopentane are each also tested asthe blowing agent. In each system, the blowing agent is added insubstantially the same molar concentration into the polyol blend. Thepolyol blend consists of commercial polyol(s), catalyst(s), andsurfactant(s). The foams are prepared in accordance with standardcommercial manufacturing operations, for example a commercial operationfor making foam for refrigeration applications. The prepared foams wereevaluated for k-factor, and this information is reported below in Table3. For benchmark, comparative purposes, foams were prepared withHFC-134a, for which commercial data can be referenced. The k-factor datafor these foams are shown in Table 6.

TABLE 6 Mean Temperature k-factor (BTU in/hr ft2 ° F.) (° F.) HFO-1234zeHFC-134a cyclopentane 40 0.127 0.146 0.143 75 0.142 0.163 0.153

This example demonstrates the k-factor performance of HFO-1234ze, andisomers thereof, when HFO-1234ze blowing agent is substituted into thepolyurethane formulation. HFO-1234ze was substituted in an equal molarconcentration to that of the benchmark foams. Table 6 data illustratesthat HFO-1234ze foams k-factors are considerably better than HFC-134a orcyclopentane foams.

Example 8 Polyurethane Foam K-Factors

This example demonstrates the performance of blowing agents comprisingHFO-1234ze (including isomers thereof) in combination with various HFCco-blowing agents used in connection with the preparation ofpolyurethane foams. The same foam formulation, equipment and proceduresused in Examples 6 and 7 are used, with the exception of the blowingagent. A blowing agent is prepared comprising HFO-1234ze (includingisomers thereof) in a concentration of approximately 80 weight percentof the total blowing agent, and HFC-245fa in a concentration ofapproximately 20 weight percent of the total blowing agent. In additionto blowing agent in accordance with the present invention, HFC-134a andcyclopentane were each also tested as the blowing agent. In each system,the blowing agent was added in substantially the same molarconcentration into the polyol blend. Foams are then formed using thisblowing agent and the k-factors of the foam are measured. Table 7 belowillustrates the k-factor performance of combinations of HFO-1234ze(including isomers thereof) when used in combination with HFC co-blowingagents.

TABLE 7 Temperature k-factor (BTU in/hr ft2 ° F.) (° F.)HFC-1234ze/HFC-245fa HFC-134a cyclopentane 40 0.129 0.146 0.143 75 0.1440.163 0.153

One unexpected result illustrated by this example is the ability toprocess HFO-1234ze, and HFC-1234ze/HFC blends in conventionalpolyurethane processing equipment. This is potentially of a greatadvantage in so far that it permits foam processing with various typesof systems and equipment, including: masterbatch type blendingequipment, gaseous blowing agent blending equipment, third streamaddition of the blowing agent, or blowing agent addition at the foamhead.

Example 9 Polyurethane Foam K-Factors

This example further demonstrates the unexpected performance of blowingagents in accordance with the present invention as used in theproduction of polyurethane foams. Three appliance polyurethane foams aremade, each one being formed using substantially the same materials,procedures and equipment, with the exception that different blowingagents are used. The polyol system is a commercially available,appliance-type formulation adapted for use with a liquid blowing agent.A foam machine is used to form the foam. The blowing agents are used inessentially equal molar concentrations. After formation, each foam iscut into samples suitable for measuring k-factors, which are found to beas indicated in the following Table 8B below. The blowing agentcomposition in weight percent on the basis of total blowing agent isdisclosed in Table 8A below:

TABLE 8A Blowing Agent A B C HFO-1234ze* 85 0 60 HFC-245fa 15 100 11Cyclopentane 0 0 29 *100% cis

TABLE 8B Mean k-factor Temperature (BTU in/hr ft² ° F.) (° F.) A B C 400.116 0.119 0.116 75 0.131 0.134 0.132 110 0.146 0.149 0.148

The results reported in Table 8B illustrate that the use of a compoundof the present invention (HFO-1234ze) in combination with cyclopentaneand HFC-245fa as co-blowing agents for thermoset foams at these levelsdid not impact in a deleterious manner the k-factor performance ofHFO-1234ze when used alone or with HFC-245fa. This is an unexpectedresult because heretofor the use of cyclopentane in substantial amountsin blowing agent formulations has had a deleterious impact on k-factorperformance.

Example 10 Polyurethane Foam K-Factors

A further experiment was performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. Theblowing agents consist of a compound in accordance with Formula II,namely, transHFCO-1233zd (CF₃CH═CHCl) in about the same mole percentageof the foamable composition as the blowing agent in Example 9. K-factorsare found to be as indicated in Table 9 below.

TABLE 9 Mean Temperature k-factor (° F.) (BTU in/hr ft² ° F.) 40 0.12775 0.143 110 0.159

Example 11 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. Theblowing agent consists of a compound in accordance with Formula II,namely, cisHFCO-1233zd (CF₃CH═CHCl) in about the same mole percentage ofthe foamable composition as the blowing agent in Example 9. Anacceptable foam is formed, and preferably K-factors are found to beapproximately equal to Example 10.

Example 12 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agent consisting of a combination of a compound in accordancewith Formula II, namely, transHFCO-1233zd (CF₃CH═CHCl) and each ofmethanol, propanol, isopropanol, butanol, isobutanol and t-butanol in a50:50 mole ratio, each combination being present in the blowing agentcomposition in about the same mole percentage of the foamablecomposition as the blowing agent in Example 9. An acceptable foam isformed, and preferably K-factors for each combination are found to beabout equal to or better than those indicated in Table 9 above.

Example 13

Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agents consisting of a combination of a compound inaccordance with Formula II, namely, cisHFCO-1233zd (CF₃CH═CHCl) and eachof methanol, propanol, isopropanol, butanol, isobutanol and t-butanol ina 50:50 mole ratio, each combination being present in the blowing agentcomposition in about the same mole percentage of the foamablecomposition as the blowing agent in Example 9. An acceptable foam isformed, and preferably K-factors for each combination are found to beabout equal to or better than those indicated in Table 9 above.

Example 14 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agents consisting of a combination of a compound inaccordance with Formula II, namely, transHFCO-1233zd (CF₃CH═CHCl) andeach of the following additional compounds: iso-pentane, normal-pentaneand cyclo-pentane. Three blowing agents are formed in combination witheach additional compound in HFCO-1233zd:additional compound mole ratiosof 25:75, 50:50, and 75:25. Each blowing agent composition is present inabout the same mole percentage of the foamable composition as theblowing agent in Example 9. An acceptable foam is formed, and preferablyK-factors for each combination are found to be about equal to or betterthan those indicated in Table 9 above.

Example 15

Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agent consisting of a combination of a compound in accordancewith Formula II, namely, cisHFCO-1233zd (CF₃CH═CHCl) and each of thefollowing additional compounds: iso-pentane, normal-pentane andcyclo-pentane. Three blowing agents are formed in combination with eachadditional compound in HFCO-1233zd:additional compound mole ratios of25:75, 50:50, and 75:25. Each blowing agent composition is present inabout the same mole percentage of the foamable composition as theblowing agent in Example 9. An acceptable foam is formed, and preferablyK-factors for each combination are found to be about equal to or betterthan those indicated in Table 9 above.

Example 16 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agents consisting of a combination of a compound inaccordance with Formula II, namely, transHFCO-1233zd (CF₃CH═CHCl) andeach of the following additional compounds: water and CO₂. Three blowingagents are formed in combination with each additional compound inHFCO-1233zd:additional compound mole ratios of 25:75, 50:50, and 75:25.Each blowing agent composition is present in about the same molepercentage of the foamable composition as the blowing agent in Example9. An acceptable foam is formed, and preferably K-factors for eachcombination are found to be about equal to or better than thoseindicated in Table 9 above.

Example 17 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agent consisting of a combination of a compound in accordancewith Formula II, namely, cisHFCO-1233zd (CF3CH═CHCl) and each of thefollowing additional compounds: water and CO₂. Three blowing agents areformed in combination with each additional compound inHFCO-1233zd:additional compound mole ratios of 25:75, 50:50, and 75:25.Each blowing agent composition is present in about the same molepercentage of the foamable composition as the blowing agent in Example9. An acceptable foam is formed, and preferably K-factors for eachcombination are found to be about equal to or better than thoseindicated in Table 9 above.

Example 18 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agent consisting of a combination of a compound in accordancewith Formula II, namely, transHFCO-1233zd (CF₃CH═CHCl) and each ofHFO-1234ye-trans(E) (having a boiling point of 15C) andHFO-1234ye-cis(Z) (having a boiling point of 24C), in combination withHFCO-1233zd in a 50:50 mole ratio, each combination being present in theblowing agent composition in about the same mole percentage of thefoamable composition as the blowing agent in Example 9. An acceptablefoam is formed, and preferably K-factors for each combination are foundto be about equal to or better than those indicated in Table 9 above.

Example 19 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agent consisting of a combination of a compound in accordancewith Formula II, namely, cisHFCO-1233zd (CF3CH═CHCl) and each ofHFO-1234ye-trans(E) (having a boiling point of 15C) andHFO-1234ye-cis(Z) (having a boiling point of 24C), in combination withHFCO-1233zd in a 50:50 mole ratio, each combination being present in theblowing agent composition in about the same mole percentage of thefoamable composition as the blowing agent in Example 9. An acceptablefoam is formed, and preferably K-factors for each combination are foundto be about equal to or better than those indicated in Table 9 above.

Example 20 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A blowingagent consisting of a combination of a compound in accordance withFormula II, namely, transHFCO-1233zd (CF₃CH═CHCl) and trans-1,2dichloroethylene, in an HFCO-1233zd:trans-1,2 dichloroethylene moleratio of 75:25, with the blowing agent composition being in about thesame mole percentage of the foamable composition as the blowing agent inExample 9. An acceptable foam is formed, and preferably K-factors foreach combination are found to be about equal to or better than thoseindicated in Table 9 above.

Example 21 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agent consisting of a combination of a compound in accordancewith Formula II, namely, cisHFCO-1233zd (CF₃CH═CHCl) and trans-1,2dichloroethylene, in an HFCO-1233zd:trans-1,2 dichloroethylene moleratio of 75:25, with the blowing agent composition being in about thesame mole percentage of the foamable composition as the blowing agent inExample 9. An acceptable foam is formed, and preferably K-factors foreach combination are found to be about equal to or better than thoseindicated in Table 9 above.

Example 22 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix, Theblowing agent consists of a combination of a compound in accordance withFormula II, namely, transHFCO-1233zd (CF₃CH═CHCl) and methyl formate, ina 75:25 mole ratio, the combination being present in the blowing agentcomposition in about the same mole percentage of the foamablecomposition as the blowing agent in Example 9. An acceptable foam isformed, and preferably K-factors are found to be about equal to orbetter than those indicated in Table 9 above.

Example 23 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix, Theblowing agent consists of a combination of a compound in accordance withFormula II, namely, cisHFCO-1233zd (CF3CH═CHCl) and methyl formate, in a75:25 mole ratio, the combination being present in the blowing agentcomposition in about the same mole percentage of the foamablecomposition as the blowing agent in Example 9. An acceptable foam isformed, and preferably K-factors are found to be about equal to orbetter than those indicated in Table 9 above.

Example 24 Polyurethane Foam K-Factors

A further experiment is performed using a similar polyol formulation andisocyanate as in Example 9, but with a different catalyst an adjuvantformulation. The foam is prepared by hand mix. The blowing agentconsists of a compound in accordance with Formula II, namely,transHFCO-1233zd (CF₃CH═CHCl) present in the blowing agent compositionin about the same mole percentage of the foamable composition as theblowing agent in Example 9. Initial K-factors are found to be asindicated in Table 10A and 7 day K-factors are as indicated in Table10B.

TABLE 10A Mean Temperature k-factor (° F.) (BTU in/hr ft² ° F.) 40 0.11575 0.127 110 0.142

TABLE 10B Mean Temperature k-factor (° F.) (BTU in/hr ft² ° F.) 40 0.11875 0.132 110 0.148

Example 25 Polyurethane Foam K-Factors

A further experiment was performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A blowingagent consisting of a compound in accordance with Formula IA, namelyHFO-1234ye-trans(E) (having a boiling point of 15C) present in theblowing agent composition in about the same mole percentage of thefoamable composition as the blowing agent in Example 9. An acceptablefoam is formed, and preferably K-factors are found to be about equal toor better than those indicated in Table 9 above.

Example 26 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A blowingagent consisting of a compound in accordance with Formula IA, namely,HFO-1234ye-cis(Z) (having a boiling point of 24C) present in the blowingagent composition in about the same mole percentage of the foamablecomposition as the blowing agent in Example 9. An acceptable foam isformed, and preferably K-factors are found to be about equal to orbetter than those indicated in Table 9 above.

Example 27 transHFCO-1233zd as Solvent

A compound of Formula II, namely, transHFCO-1233zd was transferred to aglass container. A silicon lubricant, particularly a high-viscosity(12,500 cP) silicone oil, was added to the transHFCO-1233zd solvent to aconcentration of about 10 weight percent. This resulted in ahomogeneous, single-phase solution, demonstrating that transHFCO-1233zddissolves silicone based lubricant oils.

Example 28 cisHFCO-1233zd as Solvent

A compound of Formula II, namely, cisHFCO-1233zd is transferred to aglass container. A silicon lubricant, particularly a high-viscosity(12,500 cP) silicone oil is added to the cisHFCO-1233zd solvent to aconcentration of about 10 weight percent. This results in a homogeneous,single-phase solution, demonstrating that cisHFCO-1233zd dissolvessilicone based lubricant oils.

Example 29 HFCO-1233zd/trans-1,2-dichloroethylene

A combination of transHFCO-1233zd and trans-1,2-dichloroethylene areprepared in transHFCO-1233zd:trans-1,2-dichloroethylene weight ratios of25:75 and 50:50. Each combination is then added to a glass container. Asilicon lubricant, particularly a high-viscosity (12,500 cP) siliconeoil is added to each solvent to a concentration of about 10 weightpercent. This results in a homogeneous, single-phase solution,demonstrating that this combination dissolves silicone oil to the sameor greater extent than with transHFCO-1233zd alone.

Example 30 cisHFCO-1233zd/trans-1,2-dichloroethylene

A combination of cisHFCO-1233zd and trans-1,2-dichloroethylene areprepared in cisHFCO-1233zd:trans-1,2-dichloroethylene weight ratios of25:75 and 50:50. Each combination is then added to a glass container. Asilicon lubricant, particularly a high-viscosity (12,500 cP) siliconeoil is added to each solvent to a concentration of about 10 weightpercent. This results in a homogeneous, single-phase solution,demonstrating that this combination dissolves silicone oil to the sameor greater extent than with cisHFCO-1233zd alone.

Example 31 transHFCO-1233zd as Cleaning Agent

A metal coupon was coated with rosin-based solder flux and allowed todry. The coupon was weighed and then dipped in transHFC-1233zd. Thecoupon was removed, allowed to dry and reweighed to determine how muchsolder flux was removed. In duplicate runs, an average of 25% by weightof the flux was removed.

Example 32 cisHFCO-1233zd as Cleaning Agent

A metal coupon is coated with rosin-based solder flux and allowed todry. The coupon is weighed and then dipped in cisHFC-1233zd. The couponwas removed, allowed to dry and reweighed to determine how much solderflux was removed. In duplicate runs, an average of 25% by weight of theflux is removed.

Example 33 transHFCO-1233zd/Methanol as Cleaning Agent

A metal coupon is coated with rosin-based solder flux and allowed todry. The coupon is weighed and then dipped in a composition comprisingtransHFC-1233zd and methanol in several different concentrations rangingfrom about 1% to about 10% (and even more preferably from about 1% toabout 5%), including about about 1%, about 2%, about 3%, about 5% andabout 10% by weight. The coupon is removed, allowed to dry and reweighedto determine how much solder flux is removed. In duplicate runs, anamount of flux greater than that removed in Example 31 is removed, withthe composition containing 3% by weight of methanol removing about 98%of the flux.

Example 34 cisHFCO-1233zd/Methanol as Cleaning Agent

A metal coupon is coated with rosin-based solder flux and allowed todry. The coupon is weighed and then dipped in a composition comprisingcisHFC-1233zd and methanol in several different concentrations rangingfrom about 1% to about 10% (and even more preferably from about 1% toabout 5%), including about 1%, about 2%, about 3%, about 5% and about10% by weight. The coupon is removed, allowed to dry and reweighed todetermine how much solder flux is removed. In duplicate runs, an amountof flux greater than that removed in Example 32 is removed, with thecomposition containing 3% by weight of methanol removing about 98% ofthe flux.

Example 35 trans HFCO-1233zd as Extractant

A medicament, particularly a plant-derived Artemisinin which is ananti-malarial drug, is extracted from the Artemisia annua plant. Asample of Artemisinin was weighed into a vial. A compound of Formula II,namely, transHFCO-1233zd was added to the vial until the Artemisinindissolved. The results showed that medicaments, particularlyplant-derived medicaments such as Artemisinin is soluble up toapproximately 3 weight percent in transHFCO-1233zd, demonstrating thattransHFCO-1233zd can be used to extract the drug from biomass.

Example 36 cisHFCO-1233zd as Extractant

A medicament, particularly a plant-derived Artemisinin which is ananti-malarial drug, is extracted from the Artemisia annua plant. Asample of Artemisinin was weighed into a vial. A compound of Formula II,namely, cisHFCO-1233zd was added to the vial until the Artemisinindissolved. The results showed that medicaments, particularlyplant-derived medicaments such as Artemisinin is soluble up toapproximately 3 weight percent in cisHFCO-1233zd, demonstrating thattransHFCO-1233zd can be used to extract the drug from biomass.

Example 37 transHFCO-1233zd/dichloroethylene as Extractant

Example 35 is repeated except that a combination of transHFCO-1233zd andtrans-1,2-dichloroethylene in a 50:50 weight ratio is used as theextractant. The solubility and extraction efficiency are as good as orbetter than that observed with transHFCO-1233zd alone.

Example 38 cisHFCO-1233zd/dichloroethylene as Extractant

Example 36 is repeated except that a combination of cisHFCO-1233zd andtrans-1,2-dichloroethylene in a 50:50 weight ratio is used as theextractant. The solubility and extraction efficiency are as good as orbetter than that observed with cisHFCO-1233zd alone.

Example 39 transHFCO-1233zd Combinations as Solvent

A hydrocarbon lubricant, specifically mineral oil, was added to vialscontaining, respectively, transHFCO-1233zd/methanol in an approximate98:2 weight ratio, transHFCO-1233zd/pentane in an approximate 96:4weight ration and transHFCO-1233zd/methanol/pentane in an approximate92:2:6 weight ratio. In all cases homogeneous, single-phase solutionswere formed at concentrations greater than 10% by weight of the mineraloil.

Example 40

cisHFCO-1233zd Combinations as Solvent

A hydrocarbon lubricant, specifically mineral oil, is added to vialscontaining, respectively, cisHFCO-1233zd/methanol in an approximate 98:2weight ratio, cisHFCO-1233zd/pentane in an approximate 96:4 weightration and cisHFCO-1233zd/methanol/pentane in an approximate 92:2:6weight ratio. In all cases homogeneous, single-phase solutions areformed at concentrations greater than 10% by weight of the mineral oil.

Example 41 transHFCO-1233zd as Aerosol

A sprayable aerosol was prepared by adding transHFCO-1233zd to anaerosol can, sealing the can by crimping an aerosol valve in place andadding HFC-134a propellant to a concentration of about 14% by weight ofthe 134a and about 76% by weight of transHFCO-1233zd. Hydraulic fluidwas applied to a metal coupon with a cotton swab and the coupon wasweighed. The transHFCO-1233zd-containing aerosol was sprayed onto themetal substrate for 10 seconds. The coupon was allowed to dry and wasreweighed. Approximately 60% by weight of the hydraulic fluid wasremoved.

Example 42 cisHFCO-1233zd as Aerosol

A sprayable aerosol is prepared by adding cisHFCO-1233zd to an aerosolcan, sealing the can by crimping an aerosol valve in place and addingHFC-134a propellant to a concentration of about 14% by weight of the134a and about 76% by weight of cisHFCO-1233zd. Hydraulic fluid isapplied to a metal coupon with a cotton swab and the coupon is weighed.The cisHFCO-1233zd-containing aerosol is sprayed onto the metalsubstrate for 10 seconds. The coupon is allowed to dry and wasreweighed. Approximately 60% by weight of the hydraulic fluid isremoved.

Example 43 trans HFCO-1233zd as Extractant

A compound of Formula II, namely transHFC-1233zd is demonstrated to beacceptable as a carrier and an extraction agent a fragrance,particularly a plant-derived Jasmone. Approximately 0.39 grams ofJasmone were put into a heavy walled glass tube and approximately 1.73grams of transHFC-1233zd were added to the glass tube. The tube was thenfrozen and sealed. Upon thawing the tube, it was found that the mixturehad one liquid phase. The solution contained about 20 wt. % Jasome andabout 80 wt. % transHFCO-1233zd. The results showed that fragrances,particularly plant-derived fragrances, such as Jasome is soluble up toapproximately 20 weight percent in transHFCO-1233zd, demonstrating thattransHFCO-1233zd can be used to extract and carry the fragrance.

Example 44 cisHFCO-1233zd as Extractant

A compound of Formula II, namely cisHFC-1233zd is demonstrated to beacceptable as a carrier and an extraction agent a fragrance,particularly a plant-derived Jasmone. Approximately 0.39 grams ofJasmone are put into a heavy walled glass tube and approximately 1.73grams of cisHFC-1233zd are added to the glass tube. The tube is thenfrozen and sealed. Upon thawing the tube, it is found that the mixturehad one liquid phase. The solution contains about 20 wt. % Jasmone andabout 80 wt. % cisHFCO-1233zd. The results shows that fragrances,particularly plant-derived fragrances, such as Jasmone is soluble up toapproximately 20 weight percent in cisHFCO-1233zd, demonstrating thatcisHFCO-1233zd can be used to extract and carry the fragrance.

Example 45 transHFCO-1233zd as Solvent

A synthetic lubricant, specifically polyalkyleneglycol (PAG) lubricant,and more specifically a PAG consisting essentially of 2 or moreoxypropylene groups and having a viscosity of from about 10 to about 200centistokes at about 37° C. (sold under the trade designation ND-8 byIdemitsu Kosan) are added to a vial containing transHFCO-1233zd. Ahomogeneous, single-phase solution is formed at concentrations greaterthan 10% by weight of the PAG. The properties of the synthetic lubricantND-8 are identified below in Table 11 below.

TABLE 11 ND-8 PROPERTIES Viscosity, @ Molecular Property 40° C. cStEO:PO Ratio Weight* 42.3 0:1 930 *molecular weight is Number AverageMolecular Weight

Example 46 cisHFCO-1233zd Combinations as Solvent

A synthetic lubricant, specifically polyalkyleneglycol (PAG) lubricant,and more specifically a PAG consisting essentially of 2 or moreoxypropylene groups and having a viscosity of from about 10 to about 200centistokes at about 37° C. (sold under the trade designation ND-8 byIdemitsu Kosan) are added to a vial containing cisHFCO-1233zd. Ahomogeneous, single-phase solution is formed at concentrations greaterthan 10% by weight of the PAG.

Example 47 transHFCO-1233zd Combinations as Solvent

The PAG lubricant described in Example 45 above is added to vialscontaining, respectively, transHFCO-1233zd/methanol in an approximate98:2 weight ratio, transHFCO-1233zd/pentane in an approximate 96:4weight ration and transHFCO-1233zd/methanol/pentane in an approximate92:2:6 weight ratio. In all cases homogeneous, single-phase solutionsare formed at concentrations greater than 10% by weight of the PAG oil.

Example 48 cisHFCO-1233zd Combinations as Solvent

The PAG lubricant described in Example 45 above is added to vialscontaining, respectively, cisHFCO-1233zd/methanol in an approximate 98:2weight ratio, cisHFCO-1233zd/pentane in an approximate 96:4 weightration and cisHFCO-1233zd/methanol/pentane in an approximate 92:2:6weight ratio. In all cases homogeneous, single-phase solutions areformed at concentrations greater than 10% by weight of the PAGlubricant.

Example 49 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agents consisting of a combination of a compound inaccordance with Formula II, namely, transHFCO-1233zd (CF₃CH═CHCl) andCO₂.in a supercritical and/or near supercritical state. Three blowingagents are formed in HFCO-1233zd:CO₂ mole ratios of 25:75, 50:50, and75:25. Each blowing agent composition is present in about the same molepercentage of the foamable composition as the blowing agent in Example9. An acceptable foam is formed in each case, and preferably K-factorsfor each combination are found to be about equal to or better than thoseindicated in Table 9 above.

Example 50 Polyurethane Foam K-Factors

A further experiment is performed using the same polyol formulation andisocyanate as in Example 9. The foam is prepared by hand mix. A seriesof blowing agents consisting of a combination of a compound inaccordance with Formula II, namely, cisHFCO-1233zd (CF₃CH═CHCl) andCO₂.in a supercritical and/or near supercritical state. Three blowingagents are formed in cisHFCO-1233zd:CO₂ mole ratios of 25:75, 50:50, and75:25. Each blowing agent composition is present in about the same molepercentage of the foamable composition as the blowing agent in Example9. An acceptable foam is formed for each combination, and preferablyK-factors for each combination are found to be about equal to or betterthan those indicated in Table 9 above.

Example 51 Polyurethane Foam K-Factors

A further experiment is performed by adding an amount of water to theblowing agent and/or adding the water to the foam formulation and/orabout the time of the foaming operation, to each of the examples 11-50hereof. The water is added in an amount of about 0.5% by weight, basedon the total weight of the foam formulation. An acceptable foam isformed in each case, and preferably K-factors for each such foam arefound to be about equal to or better than those indicated in Table 9above.

Example 52

This example illustrates the performance of one embodiment of thepresent invention in which a refrigerant composition comprises HFO-1234wherein a large proportion, and preferably at least about 75% by weightand even more preferably at least about 90% by weight, of the HFO-1234is HFO-1234ye (CHF₂—CF═CHF, cis- and trans-isomers). More particularly,this example is illustrative of such a composition being used as aworking fluid in a refrigerant system, High Temperature Heat Pump andOrganic Rankine Cycle system. An example of the first system is onehaving an Evaporation Temperature of about of 35° F. and a CondensingTemperature of about 150° F. For the purposes of convenience, such heattransfer systems, that is, systems having an evaporator temperature offrom about 35° F. to about 50° F. and a CT of from about 80° F. to about120° F., are referred to herein as “chiller” or “chiller AC” systems.The operation of each of such systems using R-123 for the purposes ofcomparison and a refrigeration composition of the present inventioncomprising at least about 90% by weight of HFO-1234ye is reported inTable 12 below:

TABLE 12 Chiller Temp Conditions 40° F. ET and 95° F. CT PerformanceProperty Units R-123 Trans-HFO-1234yf Cis-HFO-1234ye Capacity Rel toR-123 % 100 120% 105% COP Rel to R-123 % 100 98% 105%

As can be seen from the Table above, many of the important refrigerationsystem performance parameters are relatively close to the parameters forR-123. Since many existing refrigeration systems have been designed forR-123, or for other refrigerants with properties similar to R-123, thoseskilled in the art will appreciate the substantial advantage of a lowGWP and/or a low ozone depleting refrigerant that can be used asreplacement for R-123 or like high boiling refrigerants with relativelyminimal modifications to the system. It is contemplated that in certainembodiments the present invention provides retrofitting methods whichcomprise replacing the refrigerant in an existing system with acomposition of the present invention, preferably a compositioncomprising at least about 90% by weight and/or consists essentially ofHFO-1234 and even more preferably any one or more of cis-HFO-1234ye,trans-HFO-1234ye, and all combinations and proportions thereof, withoutsubstantial modification of the design.

Example 53

This example illustrates the performance of one embodiment of thepresent invention in which a refrigerant composition comprises HFCO-1233wherein a large proportion, and preferably at least about 75% by weightand even more preferably at least about 90% by weight, of theHFCO-1233zd is HFCO-1233zd (CF₃—CH═CHCl, cis- and trans-isomers). Moreparticularly, this example illustrates the use of such a composition asa heat transfer fluid in a refrigerant system, High Temperature HeatPump or an Organic Rankine Cycle system. An example of the first systemis one having an Evaporation Temperature of about of 35° F. and aCondensing Temperature of about 150° F. For the purposes of convenience,such heat transfer systems, that is, systems having an evaporatortemperature of from about 35° F. to about 50° F. and a CT of from about80° F. to about 120° F., are referred to herein as “chiller” or “chillerAC” systems The operation of each of such systems using R-123 and arefrigeration composition comprising at least about 90% by weight ofHFO-1233zd is reported in Table 13 below:

TABLE 13 Chiller Temp Conditions 40° F. ET and 95° F. CT PerformanceProperty Trans-HFO- Cis-HFO- Capacity Units R-123 1233zd 1233zd Rel toR-123 % 100 115%  95% COP Rel to R-123 % 100  98% 105%

As can be seen from the Table above, many of the important refrigerationsystem performance parameters are relatively close to the parameters forR-123. Since many existing refrigeration systems have been designed forR-123, or for other refrigerants with properties similar to R-123, thoseskilled in the art will appreciate the substantial advantage of a lowGWP and/or a low ozone depleting refrigerant that can be used asreplacement for R-123 or like high boiling refrigerants with relativelyminimal modifications to the system. It is contemplated that in certainembodiments the present invention provided retrofitting methods whichcomprise replacing the refrigerant in an existing system with acomposition of the present invention, preferably a compositioncomprising at least about 90% by weight and/or consists essentially ofHFO-1233 and even more preferably any one or more of cis-HFO-1233zd,trans-HFO-1233zd, and combinations of these in all proportions, withoutsubstantial modification of the design.

Example 54

This example illustrates the performance of one embodiment of thepresent invention in which a refrigerant composition comprises HFO-1234wherein a large proportion, and preferably at least about 75% by weightand even more preferably at least about 90% by weight, of the HFO-1234is HFO-1234yf. More particularly, such a composition is used as areplacement for HFC-134a in four refrigerant systems. The first systemis one have an evaporator temperature (ET) of about 20° F. and condensertemperature (CT) of about 130° F. (Example 54A). For the purposes ofconvenience, such heat transfer systems, that is, systems having an ETof from about 0 to about 35 and a CT of from about 80° F. to about 130°F., are referred to herein as “medium temperature” systems. The secondsystem is one have an ET of about −10° F. and a CT of about 110° F.(Example 54B). For the purposes of convenience, such heat transfersystems, that is, systems having an evaporator temperature of from about−20° F. to about 20° F. and a CT of from about 80° F. to about 130° F.,are referred to herein as “refrig/freezer” systems. The third system isone have an ET of about of 35° F. and a CT of about 150° F. (Example154). For the purposes of convenience, such heat transfer systems, thatis, systems having an evaporator temperature of from about 30° F. toabout 60° F. and a CT of from about 90° F. to about 200° F., arereferred to herein as “automotive AC” systems. The fourth system is onehave an ET of about 40° F. and a CT of about 60° F. (Example 54D). Forthe purposes of convenience, such heat transfer systems, that is,systems having an evaporator temperature of from about 35° F. to about50° F. and a CT of from about 80° F. to about 120° F., are referred toherein as “chiller” or “chiller AC” systems The operation of each ofsuch systems using R-134a and a refrigeration composition comprising atleast about 90% by weight of HFO-1234yf is reported in Tables 14A-Dbelow:

TABLE 14A Medium Temp Conditions 20° F. ET and 130° F. CT PerformanceProperty Units R-134a HFO-1234yf Capacity* Btu/hr 2541 2519 Rel toR-134a % 99.1% COP — 2.31 2.27 Rel to R-134a % 98.3% Discharge Press.Psig 198.7 190.3 Rel to R-134a % 95.8% Suction Press. Psig 18.4 22.5 Relto R-134a % 122.3% Mass Flow Lb/hr 0.673 0.958 Rel to R-134a % 142.3%*Capacity per CFM of compressor displacement (Volumetric Capacity)

TABLE 14B Refrig/Freezer Temp Conditions 10° F. ET and 110° F. CTPerformance Property Units R-134a HFO-1234yf Capacity* Btu/hr 1234 1293Rel to R-134a % 104.8% COP — 1.77 1.71 Rel to R-134a % 96.6% DischargePress. psig 146.4 145.4 Rel to R-134a % 99.3% Suction Press. psig 1.96.0 Rel to R-134a % 315.8% Mass Flow lb/hr 0.342 0.427 Rel to R-134a %124.9% *Capacity per CFM of compressor displacement (VolumetricCapacity)

TABLE 14C Auto AC Temp Conditions 35° F. ET and 150° F. CT PerformanceProperty Units R-134a HFO-1234yf Capacity* Btu/hr 2754 2612 Rel toR-134a % 94.8% COP — 1.91 1.84 Rel to R-134a % 96.3% Discharge Press.psig 262.9 247.3 Rel to R-134a % 94.1% Suction Press. psig 30.4 34.5 Relto R-134a % 113.5% Mass Flow lb/hr 0.891 1.235 Rel to R-134a % 138.6%*Capacity per CFM of compressor displacement (Volumetric Capacity)

TABLE 14D Chiller Temp Conditions 40° F. ET and 95° F. CT PerformanceProperty Units R-134a HFO-1234yf Capacity* Btu/hr 4236 4060 Rel toR-134a % 95.8% COP — 6.34 6.23 Rel to R-134a % 98.3% Discharge Press.psig 113.9 113.5 Rel to R-134a % 99.6% Suction Press. psig 35.0 38.7 Relto R-134a % 110.6% Mass Flow lb/hr 1.034 1.268 Rel to R-134a % 122.6%*Capacity per CFM of compressor displacement (Volumetric Capacity)

As can be seen from the Tables above, many of the importantrefrigeration system performance parameters are relatively close to theparameters for R-134a. Since many existing refrigeration systems havebeen designed for R-134a, or for other refrigerants with propertiessimilar to R-134a, those skilled in the art will appreciate thesubstantial advantage of a low GWP and/or a low ozone depletingrefrigerant that can be used as replacement for R-134a or likerefrigerants with relatively minimal modifications to the system. It iscontemplated that in certain embodiments the present invention providedretrofitting methods which comprise replacing the refrigerant in anexisting system with a composition of the present invention, preferablya composition comprising at least about 90% by weight and/or consistsessentially of HFO-1234 and even more preferably any one or more ofcis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc,HFO-1234ye(E) and HFO-1234ye(Z), without substantial modification of thesystem. In certain preferred embodiments the replacement step is adrop-in replacement in the sense that no substantial redesign of thesystem is required and no major item of equipment needs to be replacedin order to accommodate the refrigerant of the present invention.

What is claimed is:
 1. A foamable composition comprising: (i) at least one foam forming component; and (ii) a blowing agent composition comprising: (a) from 30% to 95% 99% by weight of trans-3,3,3-trifluoro1-chloro-propene (trans-HFCO-1233zd); and (b) trans-1,3,3,3-tetrafluoropropene (transHFO-1234ze).
 2. The foamable composition of claim 1 wherein 3,3,3-trifluoro, 1-chloro-propene (HFCO-1233zd) in said blowing agent consists of trans-3,3,3-trifluoro-1-chloro-propene (trans-HFCO-1233zd).
 3. The foamable composition of claim 1 wherein said blowing agent further at least one hydrocarbon selected from the group consisting of iso-pentane, normal-pentane, cyclo-pentane, butane and iso-butane and combinations of these.
 4. The foamable composition of claim 1 wherein said blowing agent further comprises trans-1,2-dichloroethylene.
 5. The foamable composition of claim 1 wherein said blowing agent further comprises dimethoxymethane.
 6. The foamable composition of claim 1 wherein the amount of (a) and (b) together comprise at least about 50% by weight of the blowing agent.
 7. The foamable composition of claim 1 wherein said blowing agent further comprises water.
 8. The foamable composition of claim 1 wherein said blowing agent further comprises CO₂.
 9. The foamable composition of claim 1 wherein said blowing agent further comprises methylformate.
 10. The foamable composition of claim 1 wherein said blowing agent further comprises from 5% to 65% by weight of at least one hydrocarbon selected from the group consisting of iso-pentane, normal-pentane, cyclo-pentane, butane and iso-butane and combinations of these.
 11. The foamable composition of claim 10 wherein said blowing agent further comprises water.
 12. The foamable composition of claim 11 wherein said water is present in an amount of from 1% to 30% by weight of the blowing agent composition.
 13. The foamable composition of claim 1 wherein said at least one foam forming component comprises a thermosetting component-capable of forming a closed cell, thermosetting foam.
 14. The foamable composition of claim 1 wherein said at least one foam forming component comprises a thermoplastic component capable of forming a closed cell, thermoplastic foam.
 15. The foamable composition of claim 14 wherein said blowing agent comprises from 30% to 70% by weight of said trans-HFO-1234ze.
 16. The foamable composition of claim 15 wherein said blowing agent comprises from 60% by weight of said trans-HFO-1233zd.
 17. The foamable composition of claim 13 wherein said at least one foam forming component is selected from the group consisting of polyurethane, polyisocyanurate, phenolics and combinations of any two or more of these.
 18. The foamable composition of claim 14 wherein said at least one foam forming component is selected from the group consisting polystyrene, polyethylene, and ethylene copolymers, polypropylene, polyethyleneterepthalate and combinations of two or more of these. 